Matt powder coatings

ABSTRACT

The invention relates to a branched carboxylic acid functional polyester resin P as described herein. The invention further relates to a thermosetting powder coating composition (PCC A) comprising a binder K, said binder K comprising the P and a crosslinker X. The invention further relates to a cured PCC A. The invention further relates to a process for making said PCC A and processes for coating an article with said PCC A. The invention further relates to an article having coated thereon said PCC A as well as to an article having coated and cured thereon said PCC A. The invention further relates to a thermosetting powder coating composition B (PCC B) comprising a physical mixture of the thermosetting powder coating composition A (PCC A) with a separate, distinct thermosetting powder coating composition A1 (PCC A1). The invention further relates to a process for making said thermosetting powder coating composition B and processes for coating an article with said PCC B. The invention further relates to a cured PCC B. The invention further relates to an article having coated thereon said thermosetting powder coating composition B as well as to an article having coated and cured thereon said thermosetting powder coating composition B. The invention further relates to use of: the polyester resin P, the PCC A, the cured PCC A, the PCC B, the cured PCC B, articles coated with the PCC A, articles coated with the PCC B, articles having coated and cured thereon the PCC A, articles having coated and cured thereon the PCC B. The invention further relates to the use of the polyester resin P for matt powder coatings. The invention further relates to the use of the PCC B for matt powder coatings.

The invention relates to a branched carboxylic acid functional polyesterresin P as described herein. The invention further relates to athermosetting powder coating composition (PCC A) comprising a binder K,said binder K comprising the P and a crosslinker X. The inventionfurther relates to a cured PCC A. The invention further relates to aprocess for making said PCC A and processes for coating an article withsaid PCC A. The invention further relates to an article having coatedthereon said PCC A as well as to an article having coated and curedthereon said PCC A. The invention further relates to a thermosettingpowder coating composition B (PCC B) comprising a physical mixture ofthe thermosetting powder coating composition A (PCC A) with a separate,distinct thermosetting powder coating composition A1 (PCC A1). Theinvention further relates to a process for making said thermosettingpowder coating composition B and processes for coating an article withsaid PCC B. The invention further relates to a cured PCC B. Theinvention further relates to an article having coated thereon saidthermosetting powder coating composition B as well as to an articlehaving coated and cured thereon said thermosetting powder coatingcomposition B. The invention further relates to use of: the polyesterresin P, the PCC A, the cured PCC A, the PCC B, the cured PCC B,articles coated with the PCC A, articles coated with the PCC B, articleshaving coated and cured thereon the PCC A, articles having coated andcured thereon the PCC B. The invention further relates to the use of thepolyester resin P for matt powder coatings. The invention furtherrelates to the use of the PCC B for matt powder coatings.

Powder coating compositions which are substantially dry, finely divided,free flowing, solid materials at room temperature and at atmosphericpressure, have gained considerable popularity in recent years overliquid coating compositions for a number of reasons. For one powdercoatings are user and environmentally friendly materials since they arevirtually free of harmful volatile organic solvents carriers that arenormally present in liquid coating compositions. Therefore, powdercoatings give off little, if any, volatile materials to the environmentwhen cured. This eliminates the solvent emission problems associatedwith liquid coating compositions such as air pollution and dangers tothe health of workers employed in coating operations. Powder coatingcompositions (or commonly also known as powders) are also clean andconvenient to use since they are applied in a clean manner over thesubstrate because they are in substantially dry solid form. The powdersare easily swept up in the event of a spill and do not require specialcleaning and spill containment supplies, as do liquid coatingcompositions. Working hygiene is thus improved. Moreover, powder coatingcompositions are essentially 100% recyclable since the sprayed powderscan be fully reclaimed and recombined with fresh powder feed. Recyclingof liquid coatings during application is often not done, which leads toincreased waste and hazardous waste disposal costs. In addition, powdercoating compositions are ready to use, i.e., no thinning or dilution isrequired.

Powder coating compositions are typically finely divided particles of apolymer, and a crosslinker in case of a thermosetting powder coatingcomposition, that also usually contain pigments, fillers, and otheradditives. After application to the substrate, the individual powderparticles are melted in an oven and coalesce to form a continuous filmtypically known as a powder coating having decorative and protectiveproperties associated with conventional organic coatings. Methods ofapplication of powder coating compositions are considered to befusion-coating processes; that is, at some time in the coating processthe powder particles must be fused or melted. Although this is usuallycarried out in a convection oven, infrared and induction heating methodshave also been used. Therefore, with minor exceptions, powder coatingsare factory applied in fixed installations, essentially excluding theiruse in maintenance applications. Powder coating compositions aretypically applied on a substrate via an electrostatic spray process; thepowder coating composition is dispersed in an air stream and passedthrough a corona discharge field where the particles acquire anelectrostatic charge. The charged particles are attracted to anddeposited on the grounded object to be coated. The object usually atroom temperature, is then placed in an oven where the powder melts andforms a powder coating. A hybrid process based on a combination of highvoltage electrostatic charging and fluidized-bed application techniques(electrostatic fluidized bed) has evolved, as well as triboelectricspray application methods. Powder coating compositions and their processof application are the preferred coating compositions and process forcoating many familiar items such as lawn and garden equipment, patio andother metal furniture, electrical cabinets, lighting, shelving and storefixtures, and many automotive components. Today, powder coatingcompositions are widely accepted, with thousands of installations in thefactories of original equipment manufacturers (OEMS) and custom coatingjob shops.

Powder coating compositions can be thermosetting or thermoplastic. Thepresent invention relates to the field of thermosetting powder coatingcompositions. The preparation of thermosetting powder coatingcompositions is described by Misev in “Powder Coatings, Chemistry andTechnology” (pp. 224-300; 1991, John Wiley).

In a variety of applications such as white goods (e.g. fridges,freezers, washing machines, dishwashers), furniture (e.g. tables,chairs), cable covers, docking stations, tractors, crane, forklifts,bulldozers, matt coatings and especially matt powder coatings arerequired. Typically, high gloss coatings are easier to achieve inrespect to matt coatings; the formulation of matt thermosetting powdercoatings poses a series of challenges for the formulator such as poorphysical and/or mechanical properties, poor storage stability of thethermosetting powder coating composition, a process for makingthermosetting powder coating compositions suitable for matt powdercoatings that is expensive and difficult to control, and inconsistencyof the matting effect of the powder coatings (large batch-to-batchvariation) and high dependency of the curing conditions of thethermosetting powder coating compositions suitable for matt powdercoatings. However, the modern challenges for the formulator of mattpowder coatings do not end here.

The typical curing temperatures of thermosetting powder coatingcompositions range from 180 to 225° C. In order to comply with morestringent environmental regulations, there has been increased attentionto the development of thermosetting powder coating compositions that canbe cured at temperatures lower than 180° C. A decrease in temperature atwhich a thermosetting powder coating composition can be cured is desiredas this is economically, environmentally and technically advantageous. Adecrease in curing temperature, while keeping the cure time constant,reduces the energy consumption, which is beneficial both from anecological and an economical point of view, rendering at the same timethis type of thermosetting powder coating compositions attractive topowder coaters since the throughput of their powder coating lines mayalso be significantly increased. Furthermore, due to a decrease of curetemperature, heat-sensitive substrates may also be used, therebybroadening the field of application for such a thermosetting powdercoating composition. Powder coatings resulting from low bakethermosetting powder coating compositions may however display poorphysical and/or mechanical properties such as for example poor reverseimpact resistance due to inadequate cure.

Therefore, the combination of matting, low bake, good storage stability,good mechanical properties such as for example good reverse impactresistance, poses a serious challenge for a formulator of thermosettingpowder coating compositions.

Therefore, there is a desire for thermosetting powder coatingcompositions that not only can be cured at lower temperatures (curing atlow temperatures is also referred to herein as low bake) and be storagestable but also have the ability to produce upon curing matt powdercoatings that have also good reverse impact resistance.

It is therefore the object of the invention to provide storage stable,low bake thermosetting powder coating compositions that upon curingprovide matt powder coatings having good reverse impact resistance(RIR).

This object is achieved by a branched carboxylic acid functionalpolyester resin P—as described herein and as defined by the claims—whichwhen used in a thermosetting powder coating composition A (PCC A)—asdescribed herein and as defined by the claims—and said PCC A is used ina thermosetting powder coating composition B (PCC B)—as described hereinand as defined by the claims—, the PCC B are storage stable, low bakeand upon curing can provide matt powder coatings having good reverseimpact resistance (RIR).

Broadly in accordance with the invention, there is provided a branchedcarboxylic acid functional polyester resin P as described herein and asdefined by the claims.

Broadly in accordance with the invention, there is provided a binder Kas described herein and as defined by the claims.

Broadly in accordance with the invention, there is provided athermosetting powder coating composition A (PCC A) as described hereinand as defined by the claims.

Broadly in accordance with the invention, there is provided athermosetting powder coating composition B (PCC B) as described hereinand as defined by the claims.

Broadly in accordance with the invention, there is provided a curedthermosetting powder coating composition A as described herein and asdefined by the claims.

Broadly in accordance with the invention, there is provided a curedthermosetting powder coating composition B, as described herein and asdefined by the claims.

Broadly in accordance with the invention, there is provided an articlehaving coated thereon a thermosetting powder coating composition A asdescribed herein and as defined by the claims.

Broadly in accordance with the invention, there is provided an articlehaving coated thereon a thermosetting powder coating composition B asdescribed herein and as defined by the claims.

Broadly in accordance with the invention, there is provided an articlehaving coated and cured thereon a thermosetting powder coatingcomposition A as described herein and as defined by the claims.

Broadly in accordance with the invention, there is provided an articlehaving coated and cured thereon a thermosetting powder coatingcomposition B as described herein and as defined by the claims.

Broadly in accordance with the invention, there is provided a processfor making an article having coated and cured thereon either athermosetting powder coating composition A as described herein and asdefined by the claims.

Broadly in accordance with the invention, there is provided a processfor making an article having coated and cured thereon either athermosetting powder coating composition B as described herein and asdefined by the claims.

Broadly in accordance with the invention, there is provided a use of:

-   -   i) a branched carboxylic acid functional polyester resin P as        described herein and as defined by the claims; or    -   ii) a thermosetting powder coating composition A as described        herein and as defined by the claims; or    -   iii) a thermosetting powder coating composition B as described        herein and as defined by the claims; or    -   iv) a cured thermosetting powder coating composition A as        described herein and as defined by the claims; or    -   v) a cured thermosetting powder coating composition B as        described herein and as defined by the claims; or    -   vi) an article as described herein and as defined by the claims;

-   in powder coatings, powder-in-mould coatings, 3D-printing,    automotive applications, marine applications, aerospace    applications, medical applications, defense applications,    sports/recreational applications, architectural applications,    bottling applications, household applications, machinery    applications, can applications, coil applications, energy    applications, textile applications and electrical applications.

Broadly in accordance with the invention there is provided a use of abranched carboxylic acid functional polyester resin P as describedherein and as defined by the claims for matt powder coatings.

Broadly in accordance with the invention there is provided a use of a athermosetting powder coating composition B as described herein and asdefined by the claims for matt powder coatings.

The P and/or the PCC A when used in a PCC B—as each of them is describedherein and as is defined by the claims—, the PCC B are storage stable,low bake and upon curing can provide matt powder coatings having goodreverse impact resistance (RIR). More particularly, the PCC B are lowbake, storage stable and upon curing provide matt powder coatings withgood reverse impact resistance.

The polyester resin P, the crosslinker X, the binder K are associatedwith the PCC A and each of them is as described herein and as defined bythe claims; sections 1-5 refer to the polyester resin P, the crosslinkerX, the binder K and the PCC A; any feature, element, component,embodiment, range and especially any preferred feature, preferredelement, preferred embodiment, preferred range, preferred combination ofranges, preferment described in sections 1-5 can be combined with eachother.

The polyester resin P1, the crosslinker X1, the binder K1 are associatedwith the PCC A1 and each of them is as described herein and as definedby the claims; sections 6-8 refer to the polyester resin P1, thecrosslinker X1, the binder K1 and the PCC A1; any feature, element,component, embodiment, range and especially any preferred feature,preferred element, preferred embodiment, preferred range, preferredcombination of ranges, preferment described in sections 6-8 can becombined with each other.

The PCC B comprises a physical mixture of the PCC A and PCC A1 and eachof them is as described herein and as defined by the claims; sections9-12 refer to the PCC B; any feature, element, component, embodiment,range and especially any preferred feature, preferred element, preferredembodiment, preferred range, preferred combination of ranges, prefermentdescribed in sections 9-12 can be combined with each other.

Definitions

A “resin” is herein understood to have the same meaning as it has to askilled person in thermosetting polymer chemistry, namely as a lowmolecular weight polymer having functional groups e.g. carboxylic acidfunctional groups ( . . . —COOH); the term “low molecular weight” meansa theoretical number average molecular weight (M_(n)) lying between afew hundred Da, e.g. 1000 Da, and a few thousand Da, e.g. 15000 Da;preferably, the number of reactive groups per molecule is at least two.The resin is able to crosslink via reactions that involve its functionalgroups, said reactions are induced by means of heat and/or radiation,ultimately connecting the polymer chains together through the formationof permanent covalent (crosslink) bonds, resulting to a cured resin.

By “polymer” is meant herein a polymer having a theoretical numberaverage molecular weight (M_(n)) higher than 15000 Da.

By “functional groups” is meant herein a covalently bonded group ofatoms within a molecule, such as for example the carboxylic acid groupin a carboxylic acid or the hydroxyl group in an alcohol or the oxiranegroup in an epoxy resin, that determines the chemical behaviour of saidcompound, are capable of reacting with functional groups of anothermolecule and are responsible for the characteristic chemical reactionsof those molecules. In the case of a carboxylic acid functionalpolyester resin the functional groups of said polyester resin arepredominantly carboxylic acid functional groups that behave as a unit inchemical reactions and said groups are capable of reacting with thefunctional groups of another molecule, for example a crosslinker such asan epoxy compound and/or an BHA compound. Typically in the case of acarboxylic acid functional polyester resin, the carboxylic acidfunctional groups are terminal groups (=end-groups) which are located atthe end(s) of the polyester resin's macromolecular structure (includingterminal groups on side chains which side chains form part of the mainand longer—when compared to side chains—macromolecular chain) of eachpolyester resin molecule.

By “polyester resin” is meant herein a resin which is the reactionproduct of a polycondensation reaction between alcohols and carboxylicacids and/or derivatives of carboxylic acids such as carboxylic acidanhydrides and esters of carboxylic acids.

In reference to the monomers used for the preparation of a polyesterresin, by the terms “monomers” or equally “monomers used for thepreparation of a polyester resin” is meant herein the total of alcoholsand the total of carboxylic acids and/or carboxylic acid anhydridesand/or esters of carboxylic acids, used for the preparation of saidpolyester resin. Obviously, the term “monomers” include the specificalcohols and carboxylic acids—as described herein and as defined by theclaims—, for example monomers include but are not limited to theneopentyl glycol, the ethylene glycol, the C₆ diol, the polyol, theisophthalic acid, the terephthalic acid, the adipic acid, thepolycarboxylic acid, the at least trifunctional monomer, that are usedto prepare the polyester resins P and P1. The total of the alcoholfunctional compounds forms the “polyalcohol constituent” of thepolyester resin and the total of the carboxylic acid functionalcompounds forms the “polyacid constituent” of the polyester resin. Thus,in the context of the invention a polyester resin is the reactionproduct of a polycondensation reaction between a polyalcohol constituentand a polyacid constituent. Any other reference to the terms “monomer”or “monomers” not associated to the monomers used for the preparation ofa polyester resin, has the same meaning as it has to a skilled person inorganic chemistry and polymer chemistry.

By “monomers used for the preparation of a polyester resin” is meantmonomers reacted to produce said polyester resin, thus said reactedmonomers represent the composition of said polyester resin.

By “mol % is based on a polyester resin ” or equally “mol % based on apolyester resin” is meant herein the total amount of moles of monomersreacted to produce said polyester resin. For clarity, the total amountof monomers reacted to produce the polyester resin is (allowing forrounding errors) 100 mol %. For example the total amount of the specificalcohols and carboxylic acids—as described herein and as defined by theclaims—that are used to prepare the polyester resins P and P1, andoptionally any other alcohol and/or carboxylic acid that may be used toprepare the polyester resins P and P1, is 100 mol %. In the context ofthe invention, any reference to “mol %” is to be construed as “mol % isbased on a polyester resin ” or equally “mol % based on a polyesterresin”.

By “mono-alcohol” is meant herein an alcohol having one hydroxyl group.

By “diol” is meant herein an alcohol having two hydroxyl groups.

By “C₆ diol” is meant herein a diol having 6 carbon atoms in itschemical structure and/or a mixture of diols each of which has 6 carbonatoms in its chemical structure.

By “polyol” is meant herein an alcohol having at least 3 hydroxylgroups; preferably the polyol has at least three and at most 10 hydroxylgroups, more preferably the polyol has at least three and at most 8hydroxyl groups, even more preferably the polyol has at least three andat most 6 hydroxyl groups, most preferably the polyol has at least threeand at most 5 hydroxyl groups, especially the polyol has at least threeand at most 4 hydroxyl groups, more especially the polyol has threehydroxyl groups or equally the polyol is a triol, for example the polyolis trimethylolpropane.

By “mono-carboxylic acid” is meant herein a carboxylic acid having onecarboxylic acid group and/or said carboxylic acid's anhydride and/or anester of a mono-carboxylic acid; preferably the mono-carboxylic acid isa carboxylic acid having one carboxylic acid group.

By “diacid” is meant herein a carboxylic acid having two carboxylic acidgroups and/or said carboxylic acid's anhydride and/or a diester of acarboxylic acid; preferably the diacid is a carboxylic acid having twocarboxylic acid groups and/or a mono-anhydride of a carboxylic acid;more preferably, the diacid is a carboxylic acid having two carboxylicacid groups.

By “polycarboxylic acid” is meant herein a carboxylic acid having atleast three carboxylic acid groups and/or a carboxylic acid anhydridehaving at least one carboxylic acid anhydride group and one carboxylicacid group, and/or an ester of a carboxylic acid, having at least threeester groups. For clarity, a carboxylic acid anhydride group should becounted as two carboxylic acid groups; in the case of an ester of acarboxylic acid having at least three ester groups, each of the estergroups should be counted as one carboxylic acid group. Thus, in apolycarboxylic acid, the sum of carboxylic acid groups (counted asmentioned in this paragraph) should be at least three; for example amonomer having an anhydride group and a carboxylic acid group is, in thecontext of the present invention, a triacid. Preferably thepolycarboxylic acid has at least 3 and at most 10 carboxylic acidgroups, more preferably the polycarboxylic acid has at least three andat most 8 carboxylic acid groups, even more preferably thepolycarboxylic acid has at least three and at most 6 carboxylic acidgroups, most preferably the polycarboxylic acid has at least three andat most 5 carboxylic acid groups, especially the polycarboxylic acid hasat least three and at most 4 carboxylic acid groups, more especially thepolycarboxylic acid has three carboxylic acid groups or equally thepolycarboxylic acid is a triacid, for example the polycarboxylic acid isa carboxylic acid anhydride having at least one carboxylic acidanhydride group and one carboxylic acid group, for example thepolycarboxylic acid is trimellitic anhydride.

By “polyhydroxycarboxylic acid” is meant herein a monomer having atleast one hydroxyl group and two carboxylic acid groups, or two hydroxylgroups and one carboxylic acid groups. In the context of the invention,a polyhydroxycarboxylic acid having more hydroxyl groups than carboxylicacid groups forms part of the polyalcohol constituent of a polyesterresin; a polyhydroxycarboxylic acid having more carboxylic acid groupsthan hydroxyl groups forms part of the polyacid constituent of apolyester resin; a polyhydroxycarboxylic acid having an equal number ofcarboxylic acid groups and hydroxyl groups forms part of the polyacidconstituent of a polyester resin.

By “an at least trifunctional monomer” is meant herein a monomerselected from the group consisting of a polyol, a polycarboxylic acid, apolyhydroxycarboxylic acid and mixtures thereof. Depending on thechemical nature of the functional groups of the at least trifunctionalmonomer, said trifunctional monomer forms part of either the polyalcoholconstituent of a polyester resin or of the polyacid constituent of apolyester resin. If for example the at least trifunctional alcohol is atriol (trifunctional alcohol), then the triol forms part of thepolyalcohol constituent of the polyester resin. If for example the atleast trifunctional monomer is a triacid, then the triacid forms part ofthe polyacid acid constituent of the polyester resin. If for example theat least trifunctional monomer is a polyhydroxycarboxylic acid havingtwo carboxylic acid groups and one hydroxyl group then thepolyhydroxycarboxylic acid forms part of the polyacid acid constituentof the polyester resin.

By “branched” polyester resin is meant herein a polyester resin having afunctionality (f) of at least 2.01 and of at most 10.

By “M_(n)” or equally “desired (targeted) M_(n)” is meant herein thetheoretical number average molecular weight that is defined as follows:

M_(n)=(Σ_(i)N_(i)M_(i))/(Σ_(i)Ni)

-   where N_(i) is the number of molecules of molecular weight M_(i). In    the context of the invention, the M_(n) is calculated by multiplying    the functionality (f)—as defined herein-with 56110 and dividing the    outcome thereof by the sum of the desired (targeted) acid value (AV)    (mg KOH/g polyester resin) and the desired (targeted) hydroxyl value    (OHV) (mg KOH/g polyester resin) according to the following equation    EQ1:

M _(n)=(56110×f)/(AV+OHV)  (EQ1)

-   If the desired (targeted) values of AV, OHV are not available, then    the M_(n) can be calculated according to EQ1 by factoring in EQ1 the    measured values of AV and OHV and wherein in this case f is    calculated from analytical data on the chemical composition of the    polyester resin, said analytical data being obtained from analytical    techniques e.g. NMR spectroscopy, well-known to one skilled in the    art.

The “functionality (f)” of a resin for example a polyester resin, of adesired (targeted) M_(n) and a desired (targeted) acid value (AV) and adesired (targeted) hydroxyl value (OHV) is calculated herein accordingto the following equation EQ2:

f=[M _(n)×(AV+OHV)]/56110  (EQ2)

-   If the desired (targeted) values of AV, OHV are not available, then    the f can be calculated from analytical data on the chemical    composition of a resin, said analytical data being obtained from    analytical techniques e.g. NMR spectroscopy, well-known to one    skilled in the art.

The desired (targeted) AV of a resin for example a polyester resin ismentioned herein also as “theoretical AV” to distinguish it from themeasured AV of a resin. The desired (targeted) OHV of a resin forexample a polyester resin is mentioned herein also as “theoretical OHV”to distinguish it from the measured OHV of a resin.

Unless otherwise stated, the terms “acid value” (AV) and “hydroxylvalue” (OHV) of a resin for example a polyester resin, refer to themeasured AV and measured OHV, respectively, of a resin. The acid value(AV) of a polyester resin (mg KOH/g polyester resin) and hydroxyl value(OHV) of a polyester resin (mg KOH/g polyester resin) of the polyesterswere measured titrimetrically according to ISO 2114-2000 and ISO4629-1978, respectively. The acid value of a resin for example apolyester resin is a measure for the amount of carboxylic acid groups inthe polyester resin whereas the hydroxyl value of a resin for example apolyester resin, is a measure for the amount of hydroxyl groups in thepolyester resin.

By “viscosity” (η) or equally “viscosity (η)” or equally “viscosity” ismeant herein the melt viscosity (in Pa·s) at 160° C. Viscositymeasurements were carried out at 160° C., on a Brookfield CAP 2000+HViscometer. The applied shear-rate was 21 s⁻¹ and a 19.05 mm spindle(cone spindle CAP-S-05 (19.05 mm, 1.8°) was used.

In the context of the invention with “carboxylic acid functionalpolyester resin” is meant a polyester resin which predominantly hascarboxylic acid functional groups. A carboxylic acid functionalpolyester resin has an acid value that is higher than its hydroxylvalue. Generally, a carboxylic acid functional polyester resin has anacid value between 14 and 120 mg KOH/g polyester resin whilst thehydroxyl value of the polyester resin is less than 13 mg KOH/g polyesterresin. For clarity, the OHV of a hydroxyl functional polyester resin ishigher than its AV. A carboxylic acid functional polyester resin may beprepared by selecting the synthesis conditions and the ratio of thepolyalcohol constituent and polyacid constituent such that there is anexcess of the polyacid constituent over the polyalcohol constituent.

In the context of the invention with “hydroxyl functional polyesterresin” is meant a polyester resin which predominantly has hydroxylfunctional groups. A hydroxyl functional polyester resin has a hydroxylvalue that is higher than its acid value.

By “crosslinker” is meant herein a compound having functional groupsthat are reactable with the carboxylic acid functional groups of apolyester resin; a crosslinker may be a monomer or a resin or a polymer;preferably a crosslinker is a monomer or a resin.

By “crosslinker X” or equally “X” is meant herein a compound havingfunctional groups that are reactable with the carboxylic acid functionalgroups of the polyester resin P; crosslinker X may be a monomer or aresin or a polymer; preferably crosslinker X is a monomer or a resin.

By “crosslinker X1” or equally “X1” is meant herein a compound havingfunctional groups that are reactable with the carboxylic acid functionalgroups of the polyester resin P1; crosslinker X1 may be a monomer or aresin or a polymer; preferably crosslinker X1 is a monomer or a resin.

By “BHA compound” is meant herein a compound having at least twoβ-hydroxyalkylamide groups; for clarity the BHA compound is not amonomer used for the preparation of a polyester resin; the BHA compoundmay be a monomer or a resin or a polymer; preferably the BHA compound isa monomer or a resin, more preferably the BHA compound is a monomer.

By “epoxy compound” is meant herein a compound having at least twooxirane groups; for clarity the epoxy compound is not a monomer used forthe preparation of a polyester resin; the epoxy compound may be amonomer or a resin or a polymer; preferably the epoxy compound is amonomer or a resin, more preferably the epoxy compound is a monomer.

By “binder” is meant herein the total of carboxylic acid functionalpolyester resins and the total of crosslinkers contained in athermosetting powder coating composition; a binder is substantially dry;preferably a binder is solid at 23° C. and at atmospheric pressure (=1atm). Preferably a binder is substantially dry and solid at 23° C. andat atmospheric pressure.

The terms “amorphous” and “crystalline” used to characterize a resin ora thermosetting powder coating composition, are informal terms used inthe art to indicate the predominant character of the relevant resin orthermosetting powder coating composition, in respect to its degree ofcrystallinity but these terms are defined more precisely herein bymelting enthalpy (ΔH_(m)) values. The term “crystalline” denotes bothcrystalline and semi-crystalline.

By “amorphous” resin e.g. polyester resin or “amorphous” thermosettingpowder coating composition, is meant herein that a resin or athermosetting powder coating composition has a melting enthalpy (ΔH_(m))lower than 40, preferably lower than 35, more preferably lower than 30,even more preferably lower than 25, most preferably lower than 20,especially lower than 15, more especially lower than 10, even moreespecially lower than 5 J/g; most especially the amorphous resin oramorphous thermosetting powder coating composition has no meltingenthalpy (ΔH_(m)), that is to say that the amorphous resin or amorphousthermosetting powder coating composition does not have a meltingtemperature (T_(m)).

By “crystalline” resin e.g. polyester resin or “crystalline”thermosetting powder coating composition, is meant herein that a resinor a thermosetting powder coating composition has a melting enthalpy(ΔH_(m)) of at least 40 J/g. In case in which a crystalline resin has aT_(g), then its T_(g) is lower than its T_(m).

By “T_(g)” is meant herein the glass transition temperature. The T_(g)is measured using DSC (Differential Scanning calorimetry) as describedherein; in case a resin for example a polyester resin or a thermosettingpowder coating composition has multiple glass transition temperaturesthen the T_(g) recorded at the higher temperature is mentioned herein asT_(g).

By “T_(m)” is meant herein the melting temperature; in case a resin forexample a polyester resin or a thermosetting powder coating compositionhas multiple meltings then the T_(m) of the melting with the largestmelting enthalpy is mentioned herein as T_(m). The T_(m) is measuredusing DSC as described herein.

By “ΔH_(m)” is meant herein the melting enthalpy. The (ΔH_(m)) ismeasured using DSC as described herein. In case a resin for example apolyester resin has more than one melting peaks then the meltingenthalpy (ΔH_(m)) values mentioned herein, refer to the total of themelting enthalpy (ΔH_(m)) said total obtained by summing up the ΔH_(m)values of each of the melting peaks.

The glass transition temperature, crystallization temperature,crystallization enthalpy, melting temperature and melting enthalpy of apolyester resin, is measured via Differential Scanning calorimetry (DSC)as explained in the Examples in the sections entitled “DSC Method” and“DSC Method-PR”. The glass transition temperature, crystallizationtemperature, crystallization enthalpy, melting temperature and meltingenthalpy of a thermosetting powder coating composition is measured viaDifferential Scanning calorimetry (DSC) as explained in the Examples inthe sections entitled “DSC Method” and “DSC Method-TPCC”.

By “composition” is meant herein the combining and/or mixture ofdistinct chemical substances and/or components to form a whole.

By “powder” is meant herein, a substantially dry solid substance at roomtemperature and at atmospheric pressure reduced to a state of fine,loose particles wherein the individual particles have preferably amaximum particle size of at most 200, more preferably of at most 180,even more preferably of at most 160, most preferably of at most 150,especially of at most 140, more especially of at most 130, mostespecially of at most 120, for example of at most 110, for example of atmost 100, for example of at most 90 μm at 23° C. and at atmosphericpressure; the individual particles have preferably a minimum particlesize of at least 10, more preferably of at least 15, even morepreferably of at least 20, most preferably of at least 25, especially ofat least 30, more especially of at least 35, most especially of at least40, for example of at least 45, for example of at least 50, for exampleof at least 60, for example of at least 70 μm at 23° C. and atatmospheric pressure. A particle is defined as a small object that: a)has mean linear dimensions as described herein after and b) behaves as awhole unit in terms of its transport and properties. The particle sizedistribution (PSD) of a powder is a list of values or a mathematicalfunction that defines the relative amounts of particles present, sortedaccording to size. The terms “particle size” and “particle sizedistribution” will be used interchangeably in the context of theinvention when used in relation to a powder. The method used to measurethe particle size of the thermosetting powder coating compositions ofthe invention is sieve analysis. According to it, the powder isseparated on sieves of different sizes. Thus, the PSD is defined interms of discrete size ranges: e.g. “weight % of sample powder hasparticle size in the range of 75 microns to 90 microns”, when sieves ofthese sizes are used.

Preferably, 90 weight % of the thermosetting powder coating compositionof the invention has a particle size in the range of 20 to 200 micron.The PSD can be determined for example by the following method: a certainamount of thermosetting powder coating composition, for example 100 g,is brought onto a Fritsch Analysette Spartan sieving apparatus equippedwith a 200 micron sieve. The sample is sieved for 15 minutes at a 2.5 mmamplitude. The fraction of the sample which remained on the sieve wasweighed after sieving. The fraction of the sample that went through thesieve (sieved fraction) is collected and is placed on a 160 micron sieveand is sieved as mentioned herein above. Once the same measurements(weighing) are performed as mentioned herein above, the same procedureis repeated using sequentially a 140, a 125, a 112, a 100, a 90, a 75, a50 and a 20 micron sieve; the last sieved fraction with a size smallerthan 20 micron is also weighed. Summing up the various weight fractions,this should yield the initial amount of sample, in this example 100 g.The various weight fractions represent the PSD as a list of valuesrepresenting the relative amounts of particles present, sorted accordingto sieves used.

By “substantially dry” is meant herein that a powder e.g. athermosetting powder composition, or a polyester resin does not compriseany deliberately added organic solvent and/or aqeous solvent e.g. wateror moisture but the powder or the polyester resin may comprise moistureabsorbed from the atmosphere in an amount of up to 30, preferably up to20, more preferably up to 10, even more preferably up to 5, mostpreferably up to 3, especially up to 2, more especially up to 1% w/wbased on the total weight of the thermosetting powder composition orthat of the polyester resin.

By “thermosetting powder coating compositions” or “powders” is meantherein, a mixture of components in the form of a powder and whichcompositions have the ability to form an irreversible crosslinkednetwork (the so-called “cured form” or “cured composition”) upon curing,preferably via heat and/or radiation curing, more preferably via heatcuring. For clarity, reference to any one of terms “thermosetting powdercoating compositions” or “powders” is to be understood as uncuredthermosetting powder coating compositions or equally uncured powders.

By “curing” or “cure” is meant herein the process of becoming “set” thatis to form an irreversibly crosslinked network (the so-called “curedform” or “cured composition”), a material that can no longer flow, bemelted or dissolved. Herein, the terms “curing” “cure” and“crosslinking” are used interchangeably. Preferably, the curing of thethermosetting powder coating composition of the invention takes placeusing heat and in that case the curing can be called “heat curing”. Forclarity, the term heat curing does not include ultraviolet (UV) orelectron beam induced curing. Optionally, a combination of heat andpressure can be used to cure the heat-curable thermosetting powdercoating compositions of the invention. In the context of the invention,the term “heat curing” does not exclude the application of pressureand/or vacuum along with heat in order to cure the heat-curablethermosetting powder coating compositions of the invention.

By “heat-curable thermosetting powder coating composition” is meantherein a thermosetting powder coating composition, said composition hasthe ability to cure upon heating. The thermosetting powder coatingcompositions described herein are heat-curable.

By “radiation-curable thermosetting powder coating composition” is meantherein a thermosetting powder coating composition, said composition hasthe ability to cure upon radiation i.e. UV and/or electron beamradiation. The thermosetting powder coating compositions describedherein may be radiation-curable.

By “heat- and/or radiation-curable thermosetting powder coatingcomposition” is meant herein a thermosetting powder coating composition,said composition has the ability to cure upon heat- and/or radiationi.e. UV and/or electron beam radiation. The thermosetting powder coatingcomposition described herein may be heat- and/or radiation curable;preferably the thermosetting powder coating compositions describedherein are heat-curable.

By “cured thermosetting powder coating composition” is meant herein anobject that is derived upon partial or full curing of a thermosettingpowder coating composition; said curing may be effected via heat and/orradiation, preferably via heat; said object may have any shape, size orform and it can for example be a film, coating; preferably the curedthermosetting powder coating composition is a powder coating.

By “powder coating” is meant herein the cured thermosetting powdercoating composition in the form of a coating. A powder coating isderived upon curing of a thermosetting powder coating composition. By“brown thermosetting powder coating compositions” is meant herein athermosetting powder coating composition having brown colour andcomprising a polyester resin, a crosslinker and a brown mixture.

By “brown mixture” is meant herein the brown mixture described in theExamples in the section entitled “Preparation of thermosetting powdercoating compositions of Table 4: General procedure”.

By “low bake thermosetting powder coating compositions” is meant hereinbrown thermosetting powder coating compositions that upon curing at 160°C. for 12 min, provide brown powder coatings having reverse impactresistance (RIR) of 40 in.-lb at a film thickness of 50±5 μm (1μm=1×10⁻⁶ m), as RIR is defined and measured herein.

By “thermosetting powder coating composition having good storagestability” is meant herein that a brown thermosetting powder coatingcomposition has a physical storage stability (PSS) of at least 5, morepreferably of at least 6, even more preferably of at least 7, on a scalefrom 1 (very poor storage stability) up to 10 (excellent storagestability), as the PSS is defined and measured herein.

By “matt powder coatings” or “equally “low gloss powder coatings” ismeant herein a brown powder coating having a thickness of 60±5 μm thatis obtained upon curing at 160° C. for 12 min of a brown thermosettingpowder coating composition, said brown powder coating having a gloss 60°of at most 38, preferably of at most 36, more preferably of at most 35,as gloss 60° is defined and measured herein.

By “powder coating having good reverse impact resistance” is meantherein a brown powder coating having a thickness of 50±5 μm that isobtained upon curing at 160° C. for 12 min of a brown thermosettingpowder coating composition, said brown powder coating is able towithstand at least 40, preferably at least 45, more preferably at least50, even more preferably at least 55, most preferably at least 60 in.-lb(1 inch/lbs=0.055997 m/kg), as the reverse impact resistance (RIR) isdefined and measured herein.

By “physical mixture” is meant herein what a skilled person in the artthermosetting powder coatings would understand, that is the elements ofthe mixture are brought and mixed together without: i) a substantialphysical transformation and/or process that involves for examplesubstantial melting, use of any liquid media e.g. organic solvent,water, able to solubilize or disperse the powders, and/or ii) chemicaltransformation and/or process that involves for example a chemicalreaction, taking place. For example the physical blending of theelements of a mixture e.g. PCC A and PCC Al are elements of PCC B, witha blender (mechanical mixing/blending) is viewed as a physical mixtureaccording to the invention, whilst the melt-extrusion of the elements ofa mixture e.g. PCC A and PCC Al are elements of PCC B, (known also asco-extrusion), is viewed as a non-physical mixture.

By “one component thermosetting powder coating composition ” or “1Kthermosetting powder coating composition” or “1K system” is herein meantthat all components of the thermosetting powder coating composition aremelt-mixed e.g. via extrusion, and form part of one homogeneous powder.

By “two component thermosetting powder coating composition ” or “2Kthermosetting powder coating composition” or “2K system” is herein meanta thermosetting powder coating composition that comprises at least twoseparate, distinct powders with different chemical compositions; the atleast two separate, distinct and different powders are each typicallyprepared via melt-mixing. The at least two separate, distinct anddifferent powders are physically mixed via for example physical blendingto afford the 2K thermosetting powder coating composition, before thelatter either being stored or applied and cured onto an article.

By “components of a thermosetting powder coating composition” is meantherein constituent elements, their preferred embodiments andcombinations thereof, that constitute part of the thermosetting powdercoating composition of the invention; said components, their preferredembodiments and combinations thereof, should be construed in view of thewhole disclosure.

Certain moieties, species, groups, repeat units, compounds, oligomers,polymers, materials, mixtures, compositions and/or formulations whichcomprise and/or are used in some or all of the invention as describedherein may exist as one or more different forms such as any of those inthe following non exhaustive list: stereoisomers (such as enantiomers(e.g. E and/or Z forms), diastereoisomers and/or geometric isomers);tautomers (e.g. keto and/or enol forms). The invention comprises and/oruses all such forms which are effective as defined herein.

By “(N)IR lamp” denotes herein both a near-IR lamp and an IR lamp.

By “lower than” is meant herein that the relevant maximum boundary valueis not included in the range.

By “higher than” is meant herein that the relevant minimum boundaryvalue is not included in the range.

The value “0” (zero) in any one of the ranges mentioned herein regardingamounts of monomers used for the preparation of polyester resins P andP1, components and/or compounds and/or ingredients of a compositiondenotes that said monomer, component and/or compound and/or ingredientdoes not need to be present in the relevant composition.

By “binder” is meant herein the total of one or more carboxylic acidfunctional polyester resins and one or more of crosslinkers.

By “pph” is meant herein weight parts per hundred weight parts.

By “pph binder” is meant herein weight parts per hundred weight parts ofbinder.

By “pph binder K” is meant herein weight parts per hundred weight partsof binder K.

By “pph binder K1” is meant herein weight parts per hundred weight partsof binder K1.

By “pph PCC A” is meant herein weight parts per hundred weight parts ofPCC A.

By “pph PCC A1” is meant herein weight parts per hundred weight parts ofPCC A1.

By “pph PCC B” is meant herein weight parts per hundred weight parts ofPCC B.

By “room temperature” is meant herein a temperature of 23° C.

By “article” is meant herein an individual object or item or element ofa class designed to serve a purpose or perform a special function andcan stand alone; the article can be in any size, form or shape. Asubstrate is an example of an article. Preferably, said article isselected from the group consisting of heat-sensitive articles, non-heatsensitive articles and combinations thereof; more preferably saidarticle is selected from the group of non-heat sensitive articles, evenmore preferably said article is selected from the group consisting ofthermoplastic composite, thermoset composite, fibre reinforcedcomposites, sandwich materials e.g. sandwich materials comprising heatsensitive foam core, metal and combinations thereof. Typical examples ofnon-heat-sensitive articles include glass, ceramic, composite, fibrecement board, or metal, for example aluminum, copper or steel articles,for instance carbon steel, where the main alloying constituent iscarbon. Carbon steel usually contains carbon 0.2 and 1.5% w/w based onthe total alloy composition and often contains other constituents suchas manganese, chromium, nickel, molybdenum, copper, tungsten, cobalt, orsilicon, depending on the desired steel properties. Steel has propertiessimilar to iron if the amount of carbon is not too high, for example notmore than 1.5% w/w based on the total alloy composition. The steel maybe surface treated (treatment with zinc, or zinc phosphate or ironphosphate etc.) or non-surface treated. Heat-sensitive articles forexample heat-sensitive substrates, include plastic articles, woodarticles for example solid wood, such as for example: hard wood, softwood, plywood; veneer, particle board, low density fibre board, mediumdensity fibreboard and high density fibreboard, OSB (Oriented StrandBoard) wood laminates, chipboard and other articles in which wood is animportant constituent, such as for example foil covered wooden articles,engineered wood, plastic modified wood, plastic articles or wood plasticcompounds (WPC); articles with cellulosic fibres, for example cardboardor paper articles; textile and leather articles. Examples of plasticarticles include unsaturated polyester resin based compositions, ABS(acrylonitril butadiene styrene), melamine-formaldehyde resins,polycarbonate, polyethylene, polypropylene, ethylene-propylene-dienemonomer (EPDM), thermoplastic olefin (TPO), polyurethane (PU),polypropylene oxide (PPO), polyethylene oxide (PEO),polyethyleneterephthalate and nylon, for example polyamide 6,6 andcombinations thereof, for example polycarbonate-ABS. Otherheat-sensitive articles include objects that are a combination of anon-heat-sensitive part such as metal parts with a heat-sensitive part,such as any one of the aforementioned for example plastic hosing withheavy metal parts, strips for example aluminium frames with heat stripsetc. The article can be a domestic furniture, such as tables, chairs,cabinets, etc., bedroom and bathroom furniture, office furniture,contract furniture such as school and child furniture, hospitalfurniture, restaurant and hotel furniture, kitchen cabinets andfurniture, (flat) panels for interior design, interior and exteriorwindows and doors, interior and exterior window frames and door frames,exterior and interior sidings and flooring, articles for automotiveapplications, such as interior car parts, wheel covers, bumpers, underthe hood parts etc., flexible flooring, sporting goods, cosmetics,audio-visual applications, such as TV sets, computer housing, phones,etc., household appliances and satellite dishes.

For all upper and lower boundaries of any parameters given herein, theboundary value is included in each range for each parameter. Allcombinations of minimum and maximum values of the parameters describedherein may be used to define the parameter ranges for variousembodiments and preferences of the invention.

In the context of the present invention unless stated to the contrary,the disclosure of alternative values for the upper or lower limit of thepermitted range of a parameter, coupled with an indication that one ofsaid values is more highly preferred than the other, is to be construedas an implied statement that each intermediate value of said parameter,lying in between the more preferred and the less preferred of saidalternatives, is itself preferred to said less preferred value and alsoto each value lying between said less preferred value and saidintermediate value.

The terms “effective”, “acceptable”, “active” and/or “suitable” (forexample with reference to any process, use, method, application,preparation, product, material, formulation, compound, composition,monomer, oligomer, polymer precursor, and/or polymers of the presentinvention and/or described herein as appropriate) will be understood torefer to those features of the invention which if used in the correctmanner provide the required properties to that which they are addedand/or incorporated to be of utility as described herein. Such utilitymay be direct for example where a material has the required propertiesfor the aforementioned uses and/or indirect for example where a materialhas use as a synthetic intermediate and/or diagnostic tool in preparingother materials of direct utility. As used herein these terms alsodenote that a functional group is compatible with producing effective,acceptable, active and/or suitable end products.

The term “comprising” as used herein means that the list thatimmediately follows is non-exhaustive and may or may not include anyother additional suitable items, for example one or more furtherfeature(s), component(s) and/or substituent(s) as appropriate. The term“comprising” will be used interchangeably with the term “containing”.“Substantially comprising” or “essentially consisting of” as used hereinmeans a component or list of component(s) is present in a given materialin an amount greater than or equal to about 90% w/w, preferably greaterthan or equal to 95% w/w, more preferably greater than or equal to 98%w/w, even more preferably greater than or equal to 99% w/w of the totalamount of the given material. The term “consisting of” as used hereinmean that the list that follows is exhaustive and does not includeadditional items.

It will be understood that the total sum of any quantities expressedherein as percentages cannot (allowing for rounding errors) exceed 100%.For example the sum of all monomers of the polyester resins P and P1,binders K and K1, thermosetting powder coating compositions PCC A andPCC A1, as well as PCC B (or part(s) of each of the above thereof)comprises may, when expressed as a weight (or other) percentage of thepolyester resins P and P1, binders K and K1, thermosetting powdercoating compositions PCC A and PCC A1, as well as PCC B (or the samepart(s) of each of the above thereof), total 100%, allowing for roundingerrors. However where a list of monomers used for the preparation ofpolyester resins P and P1 or where a list of components of binders K andK1 or where a list of components of thermosetting powder coatingcompositions PCC A, PCC A1, PCC B is non-exhaustive, the sum of thepercentage for each of such components may be less than 100% to allow acertain percentage for additional amount(s) of any additionalcomponent(s) that may not be explicitly described herein.

Unless the context clearly indicates otherwise, as used herein pluralforms of the terms herein (for example monomer, polyester resin, binder,crosslinker, thermosetting powder coating composition, component,minute) are to be construed as including the singular form and viceversa.

1. Branched Carboxylic Acid Functional Polyester Resin P

In the context of the invention, the branched carboxylic acid functionalpolyester resin P is referred herein as “P” or equally as “polyesterresin P”. Preferably, the functional groups of the polyester resin P arecarboxylic acid groups and/or carboxylic acid anhydride groups; morepreferably the functional groups of the polyester resin P are carboxylicacid groups.

The polyester resin P may be prepared according to conventionalcondensation polymerization procedures by esterification ortransesterification, optionally in the presence of customaryesterification catalysts for example dibutyltin oxide, butyl stanoicacid or tetrabutyl titanate. The preparation conditions and the—COOH/—OH ratio may be selected so as to obtain polyester resins P thathave an acid value and/or a hydroxyl value within a targeted range ofvalues. Preferably the polyester resin P is prepared in bulk without theuse of a solvent. The condensation polymerization reaction may occur ata temperature of from 100 to 350° C., preferably 290° C. or less, morepreferably from 150 to 270° C. Reaction times may range from 2 to 96hours, preferably less than 72 hours, more preferably less than 60hours. The condensation polymerization reaction is preferably carriedout in a reactor vessel (the term reactor vessel is used in the entireapplication interchangeably with the term reactor). The condensationpolymerization reaction is preferably carried out in a nitrogenatmosphere. Preferably the reactions is carried out under vacuum toremove water produced during the condensation polymerization reactionwhilst vacuum is typically applied at the last stage of the synthesis ofa polyester resin P in order to achieve the desired specifications ofthe polyester resin P. Once prepared and while still in the reactor attemperatures in the range of 130 to 240° C., the polyester resin P is ina liquid state. The polyester resin P solidifies as soon as it isbrought to a temperature below its glass transition temperature forexample when the polyester resin P is discharged from a reactor onto acooling belt which is kept at room temperature or lower temperatures oron a metal tray that may be at a room temperature or below. Typicaltemperatures of the cooling belt or tray are 15-25° C. A substantiallydry polyester resin P can be isolated in any known way including directdischarge from a reactor, from a temperature as high as for example 205°C. and as low as 140° C., any known way of spray drying, freeze drying,flashing or through devolatization after the condensation polymerizationreaction or combinations thereof.

The polyester resin P may be obtained in two-steps comprising mixing andreacting the polyacid constituent with excess of the polyalcoholconstituent to form a hydroxyl functional polyester resin (precursor ofthe polyester resin P) at the end of the first step; next, the hydroxylfunctional polyester resin is reacted further with excess of carboxylicfunctional monomers to obtain the polyester resin P.

Typically and depending on the reaction set up, one skilled in the artknows that an additional amount of alcohols e.g. diols, during thesynthesis of a polyester resin such as a polyester resin P, may benecessary to compensate for alcohol losses that may take place duringthe synthesis of a polyester resin P; one skilled in the art knows andcan easily calculate said amount of alcohols e.g. diols, given theexperimental set up, the composition of the polyester resin P, saidpolyester resin's desired (targeted) AV and desired (targeted) OHV.

If desired, additives such anti-oxidants, flow additives, triboadditives can be added to the polyester resin P whilst the polyesterresin P is in the reactor vessel and prior the polyester resin P isdischarged as mentioned herein; this addition typically takes place attemperatures in the range of 170-195° C. or in the range of 160-210° C.If said additives are mixed within the polyester resin P, a reasonableamount of time to ensure proper mixing of the additive into thepolyester resin P is carried out; for example the mixing can last from15 to 60 min at temperatures in the range of 170-195° C.; subsequently,the polyester resin P is ready for being discharged.

The branched carboxylic acid functional polyester resin P, has:

-   a. a T_(g) of at least 40° C. as measured by Differential Scanning    calorimetry (DSC) at a heating rate of 5° C./min; and-   b. an acid value (AV) of at least 65 and of at most 76.8 mg KOH/g P;    and-   c. a hydroxyl value of at most 10 mg KOH/g P; and-   d. a functionality of at least 3.5 and of at most 5; and-   said polyester resin P is the reaction product of at least the    following monomers:-   neopentyl glycol in an amount of 19-38 mol %; and-   ethylene glycol in an amount of 8-21 mol %; and-   a polyol in an amount of 0-2 mol %; and-   isophthalic acid in an amount of 0-3 mol %; and-   terephthalic acid in an amount of 38-47 mol %; and-   adipic acid in an amount of 0.01-10 mol %; and-   a polycarboxylic acid, in an amount of 6-10.2 mol %; and wherein the    mol % is based on the P and wherein the total amount of monomers    used for the preparation of the polyester resin P is 100 mol %.

The polyester resin P may be amorphous or crystalline; preferably thepolyester resin P is amorphous. Typically an amorphous polyester resinis characterized by a high degree of transparency (clarity).

The polyester resin P has an M_(n) of at least 1000 and of at most 15000Da. Preferably, the polyester resin P has an M_(n) of at least 1200,more preferably of at least 1300, even more preferably of at least 1500,most preferably of at least 1600, especially of at least 1800, moreespecially of at least 2000, even more especially of at least 2100, mostespecially of at least 2200, for example of at least 2300, for exampleof at least 2400, for example of at least 2500, for example of at least2600 Da. Preferably, the polyester resin P has an M_(n) of at most12000, more preferably of at most 10000, even more preferably of at most9000, most preferably of at most 8000, especially of at most 7000, moreespecially of at most 6000, even more especially of at most 5500, mostespecially of at most 5000, for example of at most 4500, for example ofat most 4200, for example of at most 4000, for example of at most 3800,for example of at most 3600, for example of at most 3400, for example ofat most 3200, for example of at most 3000 Da.

The polyester resin P has a T_(g) of at least 40° C. Preferably thepolyester resin P has a T_(g) of at least 45, more preferably of atleast 48, more preferably of at least 50, even more preferably of atleast 52, most preferably of at least 55, especially of at least 58,more especially of at least 59, most especially of at least 60° C.Preferably, the polyester resin P has a T_(g) of at most 120, morepreferably of at most 100, more preferably of at most 90, even morepreferably of at most 85, most preferably of at most 80, especially ofat most 78, more especially of at most 75, even more especially of atmost 70° C.

The polyester resin P has an acid value (AV) of at least 65 and of atmost 76.8 mg KOH/g P. Preferably, the polyester resin P has an acidvalue of at least 66, more preferably of at least 67, more preferably ofat least 68, even more preferably of at least 69, most preferably of atleast 70 mg KOH/g P. Preferably, the polyester resin P has an acid valueof at most 76.5, more preferably of at most 76.2, more preferably of atmost 76, even more preferably of at most 75.5, most preferably of atmost 75 mg KOH/g P.

The polyester resin P has a hydroxyl value (OHV) of at most 10 mg KOH/gP. Preferably, the polyester resin P has a hydroxyl value of at least 0,more preferably of at least 0.01, more preferably of at least 0.05, evenmore preferably of at least 0.1, most preferably of at least 0.2,especially of at least 0.5 mg KOH/g P. The polyester resin P haspreferably a hydroxyl value of at most 9, more preferably of at most 8,more preferably of at most 7, even more preferably of at most 6, mostpreferably of at most 5 mg KOH/g P. Preferably the polyester resin P hasa hydroxyl value (OHV) of at least 0 and of at most 10, more preferablyof at least 0 and of at most 8, even more preferably of at least 0 andof at most 6, most preferably more preferably of at least 0 and of atmost 5 mg KOH/g P. Preferably the polyester resin P has a hydroxyl value(OHV) of at least 0.01 and of at most 10, more preferably of at least0.01 and of at most 8, even more preferably of at least 0.01 and of atmost 6, most preferably more preferably of at least 0.01 and of at most5 mg KOH/g P.

The polyester resin P has a functionality of at least 3.5 and of at most5. Preferably, the polyester resin P has a functionality of at least3.52, more preferably of at least 3.6, more preferably of at least 3.7,even more preferably of at least 3.8, most preferably of at least 3.85.Preferably, the polyester resin P has a functionality of at most 4.9,more preferably of at most 4.8, more preferably of at most 4.6, evenmore preferably of at most 4.5, most preferably of at most 4.4,especially of at most 4.3, more especially of at most 4.2, even moreespecially of at most 4.1, most especially of at most 4.

Preferably, the polyester resin P has a viscosity of at most 150, morepreferably of at most 125, most preferably of at most 100, for exampleof at most 80, for example of at most 75, for example of at most 70, forexample of at most 65, for example of at most 60, for example of at most55, for example of at most 50 for example of at most 40 for example ofat most 30, for example of at most 25, for example of at most 20, forexample of at most 15, for example of at most 10 for example of at most5 for example of at most 3 Pa·s. Preferably, the polyester resin P has aviscosity of at least 0.001, more preferably of at least 0.01, even morepreferably of at least 0.1, most preferably of at least 1, especially ofat least 3, more especially of at least 5, even more especially of atleast 8, most especially of at least 12, for example of at least 15, forexample of at least 20, for example of at least 25, for example of atleast 30 Pa·s.

In case in which the polyester resin P is amorphous, said amorphouspolyester resin P has preferably a viscosity of at most 150, morepreferably of at most 125, most preferably of at most 100, for exampleof at most 80, for example of at most 75, for example of at most 70, forexample of at most 65, for example of at most 60, for example of at most55 Pa·s. Preferably, the amorphous polyester resin P has a viscosity ofat least 5, more preferably of at least 8, even more preferably of atleast 12,most preferably of at least 15, especially of at least 20, moreespecially of at least 25, most especially of at least 30 Pa·s. Onceprepared and while still in the reactor at temperatures in the range of130 to 240° C., the amorphous polyester resin P is in a liquid state.

In case in which the polyester resin P is crystalline, said resin haspreferably a melting temperature (T_(m)) of at least 30, more preferablyof at least 40, more preferably of at least 50, most preferably of atleast 60° C. In case in which the polyester resin P is crystalline, saidresin has preferably a melting temperature (T_(m)) of at most 180, morepreferably at most 160, even more preferably at most 140° C.

In case in which the polyester resin P is crystalline, said resin haspreferably a crystallization temperature (T_(c)) of at least 30, morepreferably of at least 40° C. In case in which the polyester resin P iscrystalline, said resin has preferably a crystallization temperature(T_(c)) of at most 180, more preferably of at most 160, even morepreferably of at most 140° C.

In case in which the polyester resin P is crystalline, said polyesterresin has preferably a melting enthalpy (ΔH_(m)) of at least 45, morepreferably of at least 50, even more preferably of at least 55, mostpreferably of at least 60, especially of at least 65 J/g. In case inwhich the polyester resin P is crystalline, said polyester resin haspreferably a melting enthalpy (ΔH_(m)) of at most 400, more preferablyof at most 300, most preferably of at most 260, especially of at most240, more especially of at most 220, most especially of at most 200, forexample of at most 180, for example of at most 160, for example of atmost 140, for example of at most 130, for example at most 120 J/g.

In case in which the polyester resin P is crystalline, said crystallinepolyester resin P has preferably a viscosity of at least 0.001, morepreferably of at least 0.01, even more preferably of at least 0.1, Pa·s.Preferably, the crystalline polyester resin P has a viscosity of at most100, more preferably of at most 50, even more preferably of at most 30,most preferably of at most 25, especially of at most 15, more especiallyof at most 10, most especially of at most 5, for example of at most 3Pa·s. Preferably, the crystalline polyester resin P has a viscosity inthe range of from 0.01 to 5 Pa·s.

Preferably, the polyester resin P is solid at 23° C. and at atmosphericpressure (=1 atm). Preferably the polyester resin P is substantiallydry. Even more preferably the polyester resin P is substantially dry andsolid at 23° C. and at atmospheric pressure.

The neopentyl glycol (2,2′-dimethyl-1,3-propanediol), used for thepreparation of polyester resin P is in an amount of at least 19 and ofat most 38 mol %. Preferably the neopentyl glycol used for thepreparation of polyester resin P is in an amount of at least 20, morepreferably in an amount of at least 22, even more preferably in anamount of at least 25, most preferably in an amount of at least 27,especially in an amount of at least 28, more especially in an amount ofat least 29, most especially in an amount of at least 30 mol % based onthe P. Preferably, the neopentyl glycol used for the preparation ofpolyester resin P is in an amount of at most 37.5, more preferably in anamount of at most 37, even more preferably in an amount of at most 36.5,most preferably in an amount of at most 36, especially in an amount ofat most 35.5, more especially in an amount of at most 35, mostespecially in an amount of at most 34.5, for example in an amount of atmost 34, for example in an amount of at most 33 mol % based on the P.

The ethylene glycol used for the preparation of polyester resin P is inan amount of at least 8 and of at most 21 mol %. Preferably the ethyleneglycol used for the preparation of polyester resin P is in an amount ofat least 8.5, more preferably in an amount of at least 9, even morepreferably in an amount of at least 9.5, most preferably in an amount ofat least 10, especially in an amount of at least 11, more especially inan amount of at least 12, most especially in an amount of at least 13,for example in an amount of at least 14, for example in an amount of atleast 15 mol % based on the P. Preferably, the ethylene glycol used forthe preparation of polyester resin P is in an amount of at most 20.5,more preferably in an amount of at most 20, even more preferably in anamount of at most 19.5, most preferably in an amount of at most 19,especially in an amount of at most 18.5, more especially in an amount ofat most 18, most especially in an amount of at most 17.5 mol % based onthe P.

The polyol used for the preparation of polyester resin P is in an amountof at least 0 and of at most 2 mol %. Preferably the polyol used for thepreparation of polyester resin P is in an amount of at least 0.01, morepreferably in an amount of at least 0.05, even more preferably in anamount of at least 0.1 mol % based on the P. Preferably, the polyol usedfor the preparation of polyester resin P is in an amount of at most 1.8,more preferably in an amount of at most 1.7, even more preferably in anamount of at most 1.6, most preferably in an amount of at most 1.4,especially in an amount of at most 1.3, more especially in an amount ofat most 1.2, most especially in an amount of at most 1.1, for example inan amount of at most 1, for example in an amount of at most 0.9, forexample in an amount of at most 0.8, for example in an amount of at most0.7, for example in an amount of at most 0.6, for example in an amountof at most 0.5, for example in an amount of at most 0.4, for example inan amount of at most 0.3, for example in an amount of at most 0.2, forexample in an amount of at most 0.15 mol % based on the P. Preferably,no polyol is used in the preparation of the polyester resin P. Examplesof polyols that may be used in the preparation of the polyester resin Pare trimethylolpropane, pentaerythritol, glycerol, dipentaerythritol,trimethylolethane. Preferably, the polyol used for the preparation ofpolyester resin P is selected from the group consisting oftrimethylolpropane, glycerol, trimethylolethane and mixtures thereof;more preferably the polyol is trimethylolpropane.

The isophthalic acid used for the preparation of polyester resin P is inan amount of at least 0 and of at most 3 mol %. Preferably theisophthalic acid used for the preparation of polyester resin P is in anamount of at most 2.8, more preferably in an amount of at most 2.6, evenmore preferably in an amount of at most 2.4, most preferably in anamount of at most 2.2, especially in an amount of at most 2, moreespecially in an amount of at most 1.8, most especially in an amount ofat most 1.6, for example in an amount of at most 1.4, for example in anamount of at most 1.2, for example in an amount of at most 1, forexample in an amount of at most 0.9, for example in an amount of at most0.8, for example in an amount of at most 0.7, for example in an amountof at most 0.5, for example in an amount of at most 0.3, for example inan amount of at most 0.2, for example in an amount of at most 0.1 mol %based on the P. Preferably, no isophthalic acid is used in thepreparation of the polyester resin P.

The terephthalic acid used for the preparation of polyester resin P isin an amount of at least 38 and of at most 47 mol %. Preferably theterephthalic acid used for the preparation of polyester resin P is in anamount of at least 38.2, more preferably in an amount of at least 38.5,even more preferably in an amount of at least 38.8, most preferably inan amount of at least 39 mol % based on the P. Preferably theterephthalic acid used for the preparation of polyester resin P is in anamount of at most 46, more preferably in an amount of at most 45, evenmore preferably in an amount of at most 44, most preferably in an amountof at most 43, especially in an amount of at most 42, more especially inan amount of at most 41.5, most especially in an amount of at most 41,for example in an amount of at most 40.5, for example in an amount of atmost 40 mol % based on the P.

The adipic acid used for the preparation of polyester resin P is in anamount of at least 0.01 and of at most 10 mol %. Preferably the adipicacid used for the preparation of polyester resin P is in an amount of atleast 0.5, more preferably in an amount of at least 1, even morepreferably in an amount of at least 1.5, most preferably in an amount ofat least 2, especially in an amount of at least 2.5, more especially inan amount of at least 2.8, even more especially in an amount of at least3, most especially in an amount of at least 3.2, for example in anamount of at least 3.4, for example in an amount of at least 3.5 mol %based on the P. Preferably, the adipic acid used for the preparation ofpolyester resin P is in an amount of at most 9, more preferably in anamount of at most 8, even more preferably in an amount of at most 7,most preferably in an amount of at most 6, especially in an amount of atmost 5.5, more especially in an amount of at most 5, most especially inan amount of at most 4.5, for example in an amount of at most 4, forexample of at most 3.9 mol % based on the P.

The polycarboxylic acid used for the preparation of polyester resin P isin an amount of at least 6 and of at most 10.2 mol %. Preferably thepolycarboxylic acid used for the preparation of polyester resin P is inan amount of at least 6.5, more preferably in an amount of at least 7,even more preferably in an amount of at least 7.5, most preferably in anamount of at least 7.6, especially in an amount of at least 7.7, moreespecially in an amount of at least 7.8 mol % based on the P.Preferably, the polycarboxylic acid used for the preparation ofpolyester resin P is in an amount of at most 10, more preferably in anamount of at most 9.5, even more preferably in an amount of at most 9.2,most preferably in an amount of at most 9, especially in an amount of atmost 8.9, more especially in an amount of at most 8.8 mol % based on theP. Examples of polycarboxylic acids that may be used in the preparationof the polyester resin P are trimellitic anhydride (TMA), pyromelliticanhydride, trimesic acid and citric acid. Preferably, the polycarboxylicacid used for the preparation of polyester resin P is TMA.

Apart from neopentyl glycol and ethylene glycol, other diols that can beused for the preparation of the polyester resin P include but are notlimited to: diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, 1,3-butylethyl propanediol,2-butyl-2-ethyl-1,3-propanediol (BEPD), 2-methyl-1,3-propanediol (MPdiol), 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol,1,3-isobutanediol, 1,2-isobutanediol, 2,3-butanediol, 2-butenediol(1,4),2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclopentanediol,1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,6-hexanediol,1,4-dimethoxy cylcohexane, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,4,4′-methylene-bis(cyclohexanol), 4,4′-isopropylidene-bis(cyclohexanol),(hydrogenated bisphenol A) 1,4-bis(hydroxymethyl)cyclohexane,1,3-bis(hydroxyethyl) cyclohexane, 1,3-bis(hydroxypropyl) cyclohexane,1,3-bis(hydroxyisopropyl) cyclohexane, dodecanediol, xylene glycol,bisphenol A/propylene oxide adducts, hydroquinone/propylene oxideadducts, and hydroquinone/ethylene oxide adducts.

Apart from isophthalic acid, terephthalic acid and adipic acid otherdiacids can be used for the preparation of the polyester resin P includebut are not limited to: 2,6-naphtalene dicarboxylic acid,4,4′-oxybisbenzoic acid, tetrahydrophthalic anhydride,cyclohexanedicarboxylic acid, succinic acid, sebacid acid, phthalicanhydride, maleic anhydride, fumaric acid, itaconic acid.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section1 can be combined with each other.

2. Thermosetting Powder Coating Composition A (PCCA)

The PCC A is as described in the entire application and as defined bythe claims.

The PCC A is a one component thermosetting powder coating composition.

The PCC A can be a heat-curable and/or radiation curable thermosettingpowder coating composition; preferably the PCC A is a heat-curablethermosetting powder coating composition.

The PCC A can be amorphous or crystalline; preferably the PCC A isamorphous.

The thermosetting powder coating composition A (PCC A) comprises abinder K in an amount of at least 10 and of at most 100 pph PCC A, saidbinder K comprising a polyester resin P and a crosslinker X.

Preferably the PCC A comprises a binder K in an amount of at least 15,more preferably of at least 20, even more preferably of at least 30,most preferably of at least 35, especially of at least 40, moreespecially of at least 45, even more especially of at least 50, mostespecially of at least 60, for example of at least 70, for example of atleast 75, for example of at least 80, for example of at least 85, forexample of at least 90, for example of at least 92, for example of atleast 94, for example of at least 96, for example of at least 97, forexample of at least 98, for example of at least 99 pph PCCA. Preferablythe PCC A comprises a binder K in an amount of at most 99, morepreferably of at most 98, even more preferably of at most 97, mostpreferably of at most 96, especially of at most 94, more especially ofat most 92, even more especially of at most 90, most especially of atmost 85, for example of at most 80, for example of at most 75, forexample of at most 70, for example of at most 60, for example of at most50, for example of at most 45, for example of at most 40, for example ofat most 35, for example of at most 30, for example of at most 20, forexample of at most 15 pph PCCA.

The binder K comprises a polyester resin P in an amount of at least 10and at most 99 pph binder K. Preferably, the binder K comprises a P inan amount of at least 15, more preferably in an amount of at least 20,even more preferably in an amount of at least 25, most preferably of atleast 30, especially in an amount of at least 35, more especially in anamount of at least 40, even more especially in an amount of at least 45most especially in an amount of at least 50 pph binder K. Preferably,the binder K comprises a P in an amount of at most 98, more preferablyin an amount of at most 97, even more preferably in an amount of at most95, most preferably of at most 93, especially in an amount of at most92, more especially in an amount of at most 90, even more especially inan amount of at most 85, most especially in an amount of at most 80, forexample in an amount of at most 75, for example in an amount of at most70, for example in an amount of at most 65, for example in an amount ofat most 60, for example in an amount of at most 55, for example in anamount of at most 50 pph binder K.

The binder K comprises a crosslinker X in an amount of at least 1 and atmost 90 pph binder. Preferably, the binder K comprises a X in an amountof at least 2, more preferably in an amount of at least 3, even morepreferably in an amount of at least 5, most preferably of at least 7,especially in an amount of at least 6, more especially in an amount ofat least 8, even more especially in an amount of at least 9, mostespecially in an amount of at least 10, for example in an amount of atleast 11, for example in an amount of at least 12, for example in anamount of at least 13, for example in an amount of at least 14, forexample in an amount of at least 15, for example in an amount of atleast 20, for example in an amount of at least 25, for example in anamount of at least 30, for example in an amount of at least 35, forexample in an amount of at least 40, for example in an amount of atleast 45, for example in an amount of at least 50 pph binder K.Preferably, the binder K comprises a X in an amount of at most 85, morepreferably in an amount of at most 80, even more preferably in an amountof at most 75, most preferably of at most 70, especially in an amount ofat most 65, more especially in an amount of at most 60, even moreespecially in an amount of at most 55, most especially in an amount ofat most 50, for example in an amount of at most 45, for example in anamount of at most 40, for example in an amount of at most 35, forexample in an amount of at most 30, for example in an amount of at most25, for example in an amount of at most 20, for example in an amount ofat most 18, for example in an amount of at most 16, for example in anamount of at most 15, for example in an amount of at most 14, forexample in an amount of at most 13, for example in an amount of at most12 for example in an amount of at most 10, for example in an amount ofat most 9, for example in an amount of at most 8, for example in anamount of at most 7 for example in an amount of at most 5 for example inan amount of at most 3, for example in an amount of at most 2 forexample in an amount of at most 1 pph binder K.

Preferably, the crosslinker X is selected from the group consisting ofBHA compounds, epoxy compounds and mixtures thereof; more preferably thecrosslinker X is selected from the group consisting of BHA compounds andepoxy compounds; even more preferably the crosslinker X is selected fromthe group consisting of BHA compounds or equally the crosslinker X is aBHA compound.

Preferably the BHA compound has at least 3 β-hydroxyalkylamide groups,even more preferably the BHA compound has at least 4 β-hydroxyalkylamidegroups, most preferably the BHA compound has at least 2 and at most 4β-hydroxyalkylamide groups, especially the BHA compound has at least 3and at most 4 β-hydroxyalkylamide groups, more especially the BHAcompound has 4 β-hydroxyalkylamide groups.

Some BHA compounds are disclosed in U.S. Pat. No. 4,727,111, U.S. Pat.No. 4,788,255, U.S. Pat. No. 4,076,917, EP 322834 and EP 473380.

Suitable examples of commercially available BHA compounds are forexample N,N,N′,N′-tetrakis-(2-hydroxyethyl)-adipamide (Primid® XL-552)and N,N,N′,N′-tetrakis-(2-hydroxypropyl)-adipamide (Primid® QM 1260)available from EMS Chemie AG. Primid® XL-552 is an example of a BHAcompound having 4 β-hydroxyalkylamide groups.

If the crosslinker X is a BHA compound, then the binder K comprises aBHA compound preferably in an amount of at least 2, more preferably inan amount of at least 3, even more preferably in an amount of at least4, most preferably in an amount of at least 5, especially in an amountof at least 6, more especially in an amount of at least 7, even moreespecially in an amount of at least 8, most especially in an amount ofat least 9, for example in an amount of at least 10 pph binder K. If thecrosslinker X is a BHA compound, then the binder K comprises a BHAcompound preferably in an amount of at most 25, more preferably in anamount of at most 20, even more preferably in an amount of at most 18,most preferably in an amount of at most 16, especially in an amount ofat most 15, more especially in an amount of at most 14, even moreespecially in an amount of at most 13 pph binder K. Preferably, if thecrosslinker X is a BHA compound, then the binder K comprises acrosslinker X in an amount of at least 9 and of at most 13 pph binder K.

If the crosslinker X is a BHA compound, then the binder K comprises apolyester resin P preferably in an amount of at least 75, morepreferably in an amount of at least 80, even more preferably in anamount of at least 82, most preferably in an amount of at least 84,especially in an amount of at least 85, more especially in an amount ofat least 86, even more especially in an amount of at least 87, mostespecially in an amount of at least 88, for example in an amount of atleast 90, for example in an amount of at least 91 pph binder K. If thecrosslinker X is a BHA compound, then the binder K comprises a polyesterresin P preferably in an amount of at most 98, more preferably in anamount of at most 97, even more preferably in an amount of at most 96,most preferably in an amount of at most 95, especially in an amount ofat most 94, more especially in an amount of at most 93, even moreespecially in an amount of at most 92, most especially in an amount ofat most 91, for example in an amount of at most 90, for example in anamount of at most 88, for example in an amount of at most 87 pph binderK. Preferably, if the crosslinker X is a BHA compound, then the binder Kcomprises a polyester resin P in an amount of at least 87 and of at most91 pph binder K.

Suitable examples of epoxy compounds include bisphenol-A resins,bisphenol-F epoxy resins, glycidylesters, triglycidylisocyanurates andcombinations thereof. It is preferred to use a an epoxy compound chosenfrom the group consisting of bisphenol-A resins, bisphenol-F epoxyresins, glycidylesters and combinations thereof. More preferably, theepoxy compound is chosen from the group consisting of bisphenol-Aresins, glycidylesters and combinations thereof. Suitable examples ofcommercially available bisphenol-A epoxy resins include Araldite®GT-7004 (Huntsman), Epikote® 1002 (Shell) and DER 662®, DER 663® and DER664® (Dow). Suitable examples of commercially available glycidylestersinclude Araldite®PT910 and Araldite®PT912. Examples oftriglycidylisocyanurates include TGIC, which is commercially availableas Araldite®PT810. Preferably, the epoxy compound is a bisphenol-A epoxyresin, e.g. Araldite® GT-7004.

The epoxy compounds can vary considerably in molecular weight. This ismost often expressed as the epoxy equivalent weight (EEW). The epoxyequivalent weight is the weight of an epoxy compound containing exactlyone mole of epoxy groups, expressed in g/mol. Preferably the EEW rangesfrom 100 to 1500, more preferably from 150 to 1200, even more preferablyfrom 200 to 900 and most preferably from 400 to 850 g/mol.

If the crosslinker X is an epoxy compound, then the binder K comprisesan epoxy compound preferably in an amount of at least 2, more preferablyin an amount of at least 3, even more preferably in an amount of atleast 4, most preferably in an amount of at least 5, especially in anamount of at least 6, more especially in an amount of at least 7, evenmore especially in an amount of at least 8, most especially in an amountof at least 9, for example in an amount of at least 10, for example inan amount of at least 11, for example in an amount of at least 12, forexample in an amount of at least 13, for example in an amount of atleast 14, for example in an amount of at least 20, for example in anamount of at least 25, for example in an amount of at least 30, forexample in an amount of at least 35, for example in an amount of atleast 40, for example in an amount of at least 45 pph binder K. If thecrosslinker X is an epoxy compound, then the binder K comprises an epoxycompound preferably in an amount of at most 70, more preferably in anamount of at most 65, even more preferably in an amount of at most 60,most preferably in an amount of at most 55, especially in an amount ofat most 50, more especially in an amount of at most 45 pph binder K.

If the crosslinker X is an epoxy compound, then the binder K comprises apolyester resin P preferably in an amount of at least 40, morepreferably in an amount of at least 45, even more preferably in anamount of at least 50 pph binder K. If the crosslinker X is an epoxycompound, then the binder K comprises a polyester resin P preferably inan amount of at most 98, more preferably in an amount of at most 97,even more preferably in an amount of at most 96, most preferably in anamount of at most 95, especially in an amount of at most 94, moreespecially in an amount of at most 93, even more especially in an amountof at most 92, most especially in an amount of at most 91, for examplein an amount of at most 90, for example in an amount of at most 89, forexample in an amount of at most 88, for example in an amount of at most87, for example in an amount of at most 86, for example in an amount ofat most 80, for example in an amount of at most 75, for example in anamount of at most 70, for example in an amount of at most 65, forexample in an amount of at most 60, for example in an amount of at most55, for example in an amount of at most 50 pph binder K.

If the crosslinker X is an epoxy compound, preferably the PCC Acomprises a catalyst to promote the crosslinking reaction of thecrosslinker X with the polyester P. Suitable catalysts include aminecontaining compounds, such as tertiary amines, phosphines, imidazoles,quaternary ammonium salts, phosphonium salts, metal salts. Specificsamples of these catalysts are tetrabutylammonium and choline chloride.These catalysts may be used either alone or in combination.

The glass transition temperature (T_(g)) of the PCC A is preferably atleast 23, more preferably at least 25, even more preferably at least 35,most preferably at least 40, especially at least 45° C. The glasstransition temperature (T_(g)) of the PCC A is preferably at most 100°C., more preferably at most 90° C., even more preferably at most 80° C.,most preferably at the most 70° C.

In case in which the PCC A has a T_(m), the T_(m) is preferably at least23, more preferably at least 25, even more preferably at least 30, mostpreferably at least 40, especially at least 45, most preferably at least50° C. The T_(m) of the PCC A is preferably at most 180° C., morepreferably at most 160° C., even more preferably at most 150, mostpreferably at most 140° C.

As is apparent to the skilled person, besides a polyester resin P, alsoother resins different than polyester resins P, for example othercarboxylic acid functional polyester resins different than polyesterresin P, may be present in the binder K; said resins different thanpolyester resins P can be amorphous or crystalline, preferably saidresins are amorphous. Preferably, the amount of a polyester resin P inthe binder K is at least 90, preferably at least 93, more preferably atleast 95, even more preferably at least 97, most preferably at least 98,especially at least 99 and more especially 100% w/w based on totalamount of resins present in the binder K.

Preferably, the binder K comprises —apart from a crosslinker X—, only apolyester resin P, as a carboxylic acid functional resin, because thisoffers simplicity in formulating.

It is advantageous to use only a polyester resin P in the PCC A as theuse of only one resin as opposed to a mixture of resins in the PCC A isless laborious and economically more attractive.

The PCC A may further comprise waxes, pigments, fillers and/or the usual(processing) additives, for example degassing agents, smoothness,appearance enhancing agents or (light) stabilizers. The pigments may beinorganic or organic. Suitable inorganic pigments include for example,titanium dioxide, zinc sulphide, zinc phosphate, mica, iron oxide and/orchromium oxide. Suitable organic pigments include for example azocompounds. Suitable fillers include for example metal oxides, silicates,carbonates and sulphates. Suitable stabilizers include for exampleprimary and/or secondary antioxidants and UV stabilizers for examplequinones, (sterically hindered) phenolic compounds, phosphonites,phosphites, thioethers and HALS (hindered amine light stabilizers).Examples of suitable degassing agents include cyclohexane dimethanolbisbenzoate, benzoin and benzoin derivatives such as for example thosedescribed in WO02/50194. Other additives, such as additives forimproving tribo-chargeability may also be added. Some of these additivesmay be added after the polyester resin P is prepared in a chemicalreactor but before the polyester resin P is discharged from the chemicalreactor. Alternatively, some of these additives may be added in thepremix of the thermosetting powder coating composition as describedabove or in the extruder for instance by liquid injection.

Any feature or preferred combination of features or preferredcombination of ranges disclosed in the present invention and regard thepolyester resin P, the crosslinker X, the binder K and the PCC A can becombined with each other.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section2 can be combined with each other.

3. Process for Making the PCC A

The PCC A may be prepared by mixing the separately weighed-outcomponents in a mixer, heat the obtained premix, for example in akneader, preferably in an extruder to obtain an extrudate, cool down theobtained extrudate until it solidifies and grind it into granules orflakes that are further ground to reduce the particle size followed byappropriate classification to obtain a thermosetting powder coatingcomposition of the right particle size.

Alternatively, the PCC A may be prepared by mixing the separatelyweighed-out crosslinker X with polyester resin P to form a premix, heatthe obtained premix, for example in a kneader, preferably in an extruderto obtain an extrudate, cool down the obtained extrudate until itsolidifies and grind it into granules or flakes that are further groundto reduce the particle size. Subsequently, mixing the rest of theseparately weighed-out components and the extrudate of the crosslinker Xwith the polyester resin P to form another premix, heat the thusobtained premix, for example in a kneader, preferably in an extruder toobtain an extrudate, cool down the obtained extrudate until itsolidifies and grind it into granules or flakes that are further groundto reduce the particle size followed by appropriate classification toobtain a thermosetting powder coating composition of the right particlesize.

Preferably, the PCC A is prepared by a process comprising the steps of:

-   a. mixing the components of the PCC A to obtain a premix;-   b. heating the premix, preferably in an extruder, to obtain an    extrudate;-   c. cooling down the extrudate to obtain a solidified extrudate; and-   d. grinding the solidified extrudate into smaller particles to    obtain the PCC A.

If the premix is heated in an extruder or mixer/kneader, it is preferredto use a temperature control in order to avoid too high temperaturesthat could lead to curing of the PCC A in the extruder. The temperatureshould be set so that a good mixing is ensured bymelting/kneading/mixing of all components to get a homogeneous mass.

Preferably, the PCC A is prepared by a process comprising the steps of:

-   a. mixing the crosslinker X with the polyester resin P to obtain a    premix 1;-   b. heating the premix 1, preferably in an extruder, to obtain an    extrudate of the crosslinker X with the polyester resin P, namely    extrudate 1;-   c. cooling down the extrudate 1 to obtain a solidified extrudate 1;    and-   d. grinding the solidified extrudate 1 into smaller particles to    obtain a mixture of the crosslinker X with the polyester resin P,    namely mixture 1; and-   e. mixing the rest of the components of the PCC A with the mixture    1, to obtain a premix 2;-   f. heating the premix 2, preferably in an extruder, to obtain an    extrudate 2;-   g. cooling down the extrudate 2 to obtain a solidified extrudate 2;    and-   h. grinding the solidified extrudate 2 into smaller particles to    obtain the PCC A.

If the premix 1 and/or 2 is/are heated in an extruder or mixer/kneader,it is preferred to use a temperature control in order to avoid too hightemperatures that could lead to curing of the PCC A in the extruder. Thetemperature should be set so that a good mixing is ensured bymelting/kneading/mixing of all components to get a homogeneous mass.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section3 can be combined with each other.

4. Cured Thermosetting Powder Coating Composition A and Process forCuring the PCC A and Object Obtainable by and/or Obtained by SaidProcess

Broadly in accordance with the invention there is provided a curedthermosetting powder coating composition A, as the thermosetting powdercoating composition A is described herein. The cured thermosettingpowder coating composition A, is derived upon curing of thethermosetting powder coating composition A, as the thermosetting powdercoating composition A is described herein. Preferably the curedthermosetting powder coating composition A is a powder coating, saidpowder coating can be a primer, top coat or an intermediate coating.

Broadly in accordance with the invention there is provided a process forcuring the PCC A comprising the steps of:

-   i) providing the PCC A; and-   ii) heating and/or radiating the PCC A to partially or fully cure    it.

Preferably step ii) above is carried out via heating.

Broadly in accordance with the invention there is provided an objectobtainable and/or obtained by the aforementioned process for curing thePCC A; said object is the cured thermosetting powder coating compositionA and said cured thermosetting powder coating composition A ispreferably a powder coating, said powder coating can be a primer, topcoat or an intermediate coating.

In case of heating the PCC A in order to cure it, the heating of the PCCA can be carried out at a temperature and for a time suitable to curethe thermosetting powder coating composition of the invention.

Heating of the PCC A may be done using conventional methods, such aswith a convection oven and/or with an (N)IR lamp and/or infrared laserand/or microwave equipment may be used to heat the PCC A.

The temperature, at which the PCC A is cured, is preferably in the rangeof 120 to 225° C., more preferably from 130 to 200° C., even morepreferably from 130 to 190° C., most preferably from 130 to 180° C.,especially from 130 to 170° C., more especially from 130 to 160° C.Preferably, the temperature at which the PCC A is cured is preferably atmost 225, more preferably at most 200, even more preferably at most 190,most preferably at most 180, most preferably at most 170, especially atmost 160, more especially at most 150° C. Preferably, the temperature atwhich the thermosetting powder coating compositions of the invention arecured, is preferably at least 120, more preferably at least 130, evenmore preferably at least 135, most preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155° C.

Preferably the curing time of the PCC A is at most 60, more preferablyis at most 45, even more preferably is at most 30, most preferably is atmost 20, especially is at most 15, more especially is at most 12, evenmore especially is at most 10, most especially is at most 5 minutes.

Preferably the PCC A is cured at a temperature in the range of 130-180°C. for a time in the range of 5-30 minutes, more preferably the PCC A iscured at a temperature in the range of 130-170° C. for a time in therange of 5-30 minutes.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section4 can be combined with each other.

5. Process for Coating an Article with the PCC A and a Process forCoating and Curing an Article Having the PCC A Coated and Cured Thereon

Broadly in accordance with the invention there is provided a process forcoating an article with the PCC A comprising the step of applying thePCC A to an article as said article is defined herein, to obtain thecoated article.

Broadly in accordance with the invention there is provided a process formaking an article having coated and cured thereon a thermosetting powdercoating composition A, comprising the steps of:

-   a. applying the PCC A to an article as said article is defined    herein;-   b. heating and/or radiating the thermosetting powder coating    composition for enough time (curing time) and at a suitable    temperature to partially or fully cure (curing temperature) the PCC    A to obtain the article having coated and cured thereon the    thermosetting powder coating composition A.

Preferably, step b. above is carried out via heating.

The PCC A may be applied to an article using the techniques known to theperson skilled in the art, for example using electrostatic spray orelectrostatic fluidized bed or flame spray.

Heating of the coated substrate may be done using conventional methods,such as with a convection oven and/or with an (N)IR lamp. Even microwaveequipment may be used to heat the substrate.

The temperature, at which the PCC A is cured, is preferably in the rangeof 120 to 225° C., more preferably from 130 to 200° C., even morepreferably from 130 to 190° C., most preferably from 130 to 180° C.,especially from 130 to 170° C., more especially from 130 to 160° C.Preferably, the temperature at which the PCC A is cured is preferably atmost 225, more preferably at most 200, even more preferably at most 190,most preferably at most 180, most preferably at most 170, especially atmost 160, more especially at most 150° C. Preferably, the temperature atwhich the thermosetting powder coating compositions of the invention arecured, is preferably at least 120, more preferably at least 130, evenmore preferably at least 135, most preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155° C.

Preferably the curing time of the PCC A is at most 60, more preferablyis at most 45, even more preferably is at most 30, most preferably is atmost 20, especially is at most 15, more especially is at most 12, evenmore especially is at most 10, most especially is at most 5 minutes.

Preferably the PCC A is cured at a temperature in the range of 130-170°C. for a time in the range of 5-30 minutes.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section5 can be combined with each other.

6. Branched Carboxylic Acid Functional Polyester Resin P1

In the context of the invention, the branched carboxylic acid functionalpolyester resin P1 used in PCC A1, is referred herein as “P1” or equallyas “polyester resin P1”. Preferably, the functional groups of thepolyester resin P1 are carboxylic acid groups and/or carboxylic acidanhydride groups; more preferably the functional groups of the polyesterresin P1 are carboxylic acid groups.

The polyester resin P1 may be prepared according to conventionalcondensation polymerization procedures by esterification ortransesterification, optionally in the presence of customaryesterification catalysts for example dibutyltin oxide, butyl stanoicacid or tetrabutyl titanate. The preparation conditions and the—COOH/—OH ratio may be selected so as to obtain polyester resins P1 thathave an acid value and/or a hydroxyl value within a targeted range ofvalues. Preferably the polyester resin P1 is prepared in bulk withoutthe use of a solvent. The condensation polymerization reaction may occurat a temperature of from 100 to 350° C., preferably 290° C. or less,more preferably from 150 to 270° C. Reaction times may range from 2 to96 hours, preferably less than 72 hours, more preferably less than 60hours. The condensation polymerization reaction is preferably carriedout in a reactor. The condensation polymerization reaction is preferablycarried out in a nitrogen atmosphere. Preferably the final part of thereaction is carried out under vacuum to remove water produced during thecondensation polymerization reaction. Once prepared and while still inthe reactor at temperatures in the range of 130 to 240° C., thepolyester resin P1 is in a liquid state. The polyester resin P1solidifies as soon as it is brought to a temperature below its glasstransition temperature for example when the P1 resin is discharged froma reactor onto a cooling belt which is kept at room temperature or lowertemperatures or on a metal tray that may be at a room temperature orbelow. Typical temperatures of the cooling belt or tray are 15-25° C. Asubstantially dry polyester resin P1 can be isolated in any known wayincluding direct discharge from a reactor, from a temperature as high asfor example 180° C. to ambient temperature for example 23° C., any knownway of spray drying, freeze drying, flashing or through devolatizationafter the condensation polymerization reaction or combinations thereof.

The polyester resin P1 may be obtained in two-steps comprising mixingand reacting the polyacid constituent with excess of the polyalcoholconstituent to form a hydroxyl functional polyester resin (precursor ofthe polyester resin P1) at the end of the first step; next, the hydroxylfunctional polyester resin is reacted further with excess of carboxylicfunctional monomers to obtain the polyester resin P1.

Typically and depending on the reaction set up, one skilled in the artknows that an additional amount of alcohols e.g. diols, during thesynthesis of a polyester resin such as a polyester resin P1, may benecessary to compensate for alcohol losses that may take place duringthe synthesis of a polyester resin P1; one skilled in the art knows andcan easily calculate said amount of alcohols e.g. diols, given theexperimental set up, the composition of the polyester resin P1, saidpolyester resin's desired (targeted) AV and desired (targeted) OHV.

If desired, additives such anti-oxidants, flow additives, triboadditives can be added to the polyester resin P1 whilst the polyesterresin P1 is in the reactor vessel and prior the polyester resin P1 isdischarged as mentioned herein; this addition typically takes place attemperatures in the range of 170-195° C. If said additives are mixedwithin the polyester resin P1 a reasonable amount of time to ensureproper mixing of the additive into the polyester resin P1 is carriedout; for example the mixing can last from 15 to 60 min at temperaturesin the range of 170-195° C.; subsequently, the polyester resin P1 isready for being discharged.

The branched carboxylic acid functional polyester (P1), has:

-   a. a T_(g) of at least 40° C. as measured by Differential Scanning    calorimetry (DSC) at a heating rate of 5° C./min; and-   b. an acid value (AV) of at least 19 and of at most 35 mg KOH/g P1;    and-   c. a hydroxyl value of at most 7 mg KOH/g P1; and-   d. a functionality of at least 2.1 and of at most 3; and-   said polyester resin P1 is the reaction product of at least the    following monomers:-   neopentyl glycol in an amount of at least 31 and of at most 50 mol    %; and-   ethylene glycol in an amount of at least 2.5 and of at most 20 mol    %; and-   a C₆ diol in an amount of at least 1.1 and of at most 4.9 mol %; and-   isophthalic acid in an amount of at least 0 and of at most 6.5 mol    %; and-   terephthalic acid in an amount of at least 39 and of at most 48 mol    %; and-   adipic acid in an amount of at least 1 and of at most 10 mol %; and-   an at least trifunctional monomer in an amount of at least 0.001 and    of at most 3 mol %; and    -   wherein the mol % is based on the polyester resin P1 and wherein        the total amount of monomers used for the preparation of the        polyester resin P1 is 100 mol %.

The polyester resin P1 may be amorphous or crystalline; preferably thepolyester resin P1 is amorphous. Typically an amorphous polyester resinis characterized by a high degree of transparency (clarity).

The polyester resin P1 has an M_(m) of at least 1000 and of at most15000 Da. Preferably, the polyester resin P1 has an M_(m) of at least1200, more preferably of at least 1300, even more preferably of at least1500, most preferably of at least 1600, especially of at least 1800,more especially of at least 2000, even more especially of at least 2100,most especially of at least 2200, for example of at least 2500, forexample of at least 2800 for example of at least 3000 for example of atleast 3200 for example of at least 3500 for example of at least 3800forexample of at least 4000, for example of at least 4100 Da. Preferably,the polyester resin P1 has an M_(n) of at most 12000, more preferably ofat most 10000, even more preferably of at most 9000, most preferably ofat most 8000, especially of at most 7500, more especially of at most7000, even more especially of at most 6500, most especially of at most6200, for example of at most 6000 Da.

The polyester resin P1 has a T_(g) of at least 40° C. Preferably thepolyester resin P1 has a T_(g) of at least 45, more preferably of atleast 48, more preferably of at least 50, even more preferably of atleast 52° C. Preferably, the polyester resin P1 has a T_(g) of at most120, more preferably of at most 100, more preferably of at most 90, evenmore preferably of at most 85, most preferably of at most 80, especiallyof at most 78, more especially of at most 75, even more especially of atmost 70, most especially of at most 68, for example of at most 65, forexample of at most 62° C.

The polyester resin P1 has an acid value (AV) of at least 19 and of atmost 35 mg KOH/g P1. Preferably, the polyester resin P1 has an acidvalue of at least 19.5, more preferably of at least 19.8, morepreferably of at least 20, even more preferably of at least 21, mostpreferably of at least 22, especially of at least 23, more especially ofat least 23.5 mg KOH/g P1. Preferably, the polyester resin P1 has anacid value of at most 33, more preferably of at most 32, more preferablyof at most 30, even more preferably of at most 29, most preferably of atmost 28.5, especially of at most 28, more especially of at most 27.5 mgKOH/g P1.

The polyester resin P1 has a hydroxyl value (OHV) of at most 7 mg KOH/gP1. Preferably, the polyester resin P1 has a hydroxyl value of at least0, more preferably of at least 0.01, more preferably of at least 0.05,even more preferably of at least 0.1, most preferably of at least 0.2,especially of at least 0.5, more especially of at least 1 mg KOH/g P1.The polyester resin P1 has preferably a hydroxyl value of at most 6,more preferably of at most 5, most preferably of at most 4.9, especiallyof at most 4.5, more especially of at most 4.2, even more especially ofat most 4 mg KOH/g P1.

The polyester resin P1 has a functionality of at least 2.1 and of atmost 3. Preferably, the polyester resin P1 has a functionality of atleast 2.15, more preferably of at least 2.2, more preferably of at least2.25, even more preferably of at least 2.28. Preferably, the polyesterresin P1 has a functionality of at most 2.95, more preferably of at most2.9, more preferably of at most 2.8, even more preferably of at most2.7, most preferably of at most 2.6, especially of at most 2.55, moreespecially of at most 2.5, even more especially of at most 2.48.

Preferably, the polyester resin P1 has a viscosity of at most 150, morepreferably of at most 125, most preferably of at most 100, for exampleof at most 80, for example of at most 75, for example of at most 70, forexample of at most 65, for example of at most 60, for example of at most55, for example of at most 50 for example of at most 40 for example ofat most 30, for example of at most 25, for example of at most 20, forexample of at most 15, for example of at most 10 for example of at most5 for example of at most 3 Pa·s. Preferably, the polyester resin P1 hasa viscosity of at least 0.001, more preferably of at least 0.01, evenmore preferably of at least 0.1, most preferably of at least 1,especially of at least 3, more especially of at least 5, even moreespecially of at least 8, most especially of at least 12, for example ofat least 15, for example of at least 20, for example of at least 25, forexample of at least 30 Pa·s.

In case in which the polyester resin P1 is amorphous, said amorphouspolyester resin P1 has preferably a viscosity of at most 150, morepreferably of at most 125, most preferably of at most 100, for exampleof at most 80, for example of at most 75, for example of at most 70, forexample of at most 65, for example of at most 60, for example of at most55 Pa·s. Preferably, the amorphous polyester resin P1 has a viscosity ofat least 5, more preferably of at least 8, even more preferably of atleast 12, most preferably of at least 15, especially of at least 20,more especially of at least 25, most especially of at least 30 Pa·s.

In case in which the polyester resin P1 is crystalline, said resin haspreferably a melting temperature (T_(m)) of at least 30, more preferablyof at least 40, more preferably of at least 50, most preferably of atleast 60° C. In case in which the polyester resin P1 is crystalline,said resin has preferably a melting temperature (T_(m)) of at most 200,more preferably at most 180, even more preferably at most 160° C.

In case in which the polyester resin P1 is crystalline, said resin haspreferably a crystallization temperature (T_(c)) of at least 30, morepreferably of at least 40° C. In case in which the polyester resin P1 iscrystalline, said resin has preferably a crystallization temperature (TOof at most 200, more preferably of at most 180, even more preferably ofat most 160, even more preferably of at most 140° C.

In case in which the polyester resin P1 is crystalline, said polyesterresin has preferably a melting enthalpy (ΔH_(m)) of at least 45, morepreferably of at least 50, even more preferably of at least 55, mostpreferably of at least 60, especially of at least 65 J/g. In case inwhich the polyester resin P1 is crystalline, said polyester resin haspreferably a melting enthalpy (ΔH_(m)) of at most 400, more preferablyof at most 300, most preferably of at most 260, especially of at most240, more especially of at most 220, most especially of at most 200, forexample of at most 180, for example of at most 160, for example of atmost 140, for example of at most 130, for example at most 120 J/g.

In case in which the polyester resin P1 is crystalline, said crystallinepolyester resin P1 has preferably a viscosity of at least 0.001, morepreferably of at least 0.01, even more preferably of at least 0.1, Pa·s.Preferably, the crystalline polyester resin P1 has a viscosity of atmost 100, more preferably of at most 50, even more preferably of at most30, most preferably of at most 25, especially of at most 15, moreespecially of at most 10, most especially of at most 5, for example ofat most 3 Pa·s. Preferably, the crystalline polyester resin P1 has aviscosity in the range of from 0.01 to 5 Pa·s.

Preferably, the polyester resin P1 is solid at 23° C. and at atmosphericpressure (=1 atm). Preferably the polyester resin P1 is substantiallydry. Even more preferably the polyester resin P1 is substantially dryand solid at 23° C. and at atmospheric pressure.

The neopentyl glycol (2,2′-dimethyl-1,3-propanediol), used for thepreparation of polyester resin P1 is in an amount of at least 25 and ofat most 50 mol %. Preferably the neopentyl glycol used for thepreparation of polyester resin P1 is in an amount of at least 25.5, morepreferably in an amount of at least 26, even more preferably in anamount of at least 26.5, most preferably in an amount of at least 26.8,mol % based on the P1. Preferably, the neopentyl glycol used for thepreparation of polyester resin P1 is in an amount of at most 48, morepreferably in an amount of at most 46, even more preferably in an amountof at most 44, most preferably in an amount of at most 42, especially inan amount of at most 40, more especially in an amount of at most 39,most especially in an amount of at most 38, for example in an amount ofat most 37, for example in an amount of at most 36.5 mol % based on theP1.

The ethylene glycol used for the preparation of polyester resin P1 is inan amount of at least 2.5 and of at most 20 mol %. Preferably theethylene glycol used for the preparation of polyester resin P1 is in anamount of at least 3, more preferably in an amount of at least 4, evenmore preferably in an amount of at least 5, most preferably in an amountof at least 6, especially in an amount of at least 7, more especially inan amount of at least 8, most especially in an amount of at least 8.5,for example in an amount of at least 9, for example in an amount of atleast 9.5, for example in an amount of at least 9.8, for example in anamount of at least 10 mol % based on the P1. Preferably, the ethyleneglycol used for the preparation of polyester resin P1 is in an amount ofat most 19.5, more preferably in an amount of at most 19, even morepreferably in an amount of at most 18.8, most preferably in an amount ofat most 18.6, especially in an amount of at most 18.4 mol % based on theP1.

The C₆ diol can be a linear, cyclic, saturated, unsaturated andcombinations thereof. Preferably the C₆ diol is linear, more preferablythe C₆ diol is linear and saturated. Examples of C₆ diol that may beused in the preparation of the polyester resin P1 include but are notlimited to 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol,1,3-hexanediol, 1,2-hexanediol, 2,3-hexanediol, 2,4-hexanediol,2,5-hexanediol, 3,4-hexanediol, 2-ethyl-1,4-butanediol,2,3-dimethyl-1,4-butanediol, 2,3-dimethyl-2,3-butanediol,2-hexene-1,6-diol, 3-hexene-1,6-diol, 2-hexene-1,5-diol, dipropyleneglycol, 1,4-cyclohexanediol, 1,4-benzenediol. Preferably, the C₆ diolused for the preparation of polyester resin P1 is selected from thegroup consisting of 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol,2,5-hexanediol 1,3-hexanediol, 1,2-hexanediol, 2-ethyl-1,3-hexanedioland mixtures thereof, more preferably the C₆ diol used for thepreparation of polyester resin P1 is selected from the group consistingof 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol and 2,5-hexanediol andmixtures thereof, even more preferably the C₆ diol used for thepreparation of polyester resin P1 is selected from the group consistingof 1,6-hexanediol, 1,5-hexanediol and mixtures thereof, most preferablythe C₆ diol used for the preparation of polyester resin P1 is1,6-hexanediol.

The C₆ diol used for the preparation of polyester resin P1 is in anamount of at least 1.1 and of at most 4.9 mol %. Preferably, the C₆ diolused for the preparation of polyester resin P1 is in an amount of atleast 1.2, more preferably in an amount of at least 1.5, even morepreferably in an amount of at least 1.8, most preferably in an amount ofat least 2, especially in an amount of at least 2.2, more especially inan amount of at least 2.4, even more especially in an amount of at least2.6, most especially in an amount of at least 2.7, for example in anamount of at least 2.8, for example in an amount of at least 2.85 mol %based on the P1. Preferably, the C₆ diol used for the preparation ofpolyester resin P1 is in an amount of at most 4.8, more preferably in anamount of at most 4.7, even more preferably in an amount of at most 4.6,most preferably in an amount of at most 4.5, especially in an amount ofat most 4.4, more especially in an amount of at most 4.2, mostespecially in an amount of at most 4.1, for example in an amount of atmost 4, for example in an amount of at most 3.9, for example in anamount of at most 3.8, for example in an amount of at most 3.7, forexample in an amount of at most 3.6, for example in an amount of at most3.5, for example in an amount of at most 3.4, for example in an amountof at most 3.3, for example in an amount of at most 3.2 mol % based onthe P1.

The isophthalic acid used for the preparation of polyester resin P1 isin an amount of at least 0 and of at most 6.5 mol %. Preferably theisophthalic acid used for the preparation of polyester resin P1 is in anamount of at least 0.1, more preferably in an amount of at least 0.5,even more preferably in an amount of at least 0.8, most preferably in anamount of at least 1, especially in an amount of at least 1.5, moreespecially in an amount of at least 1.8, most especially in an amount ofat least 2, for example in an amount of at least 2.2, for example in anamount of at least 2.5, for example in an amount of at most 2.8, forexample in an amount of at least 3, for example in an amount of at least3.2, for example in an amount of at least 3.5, for example in an amountof at least 3.8, for example in an amount of at least 4, for example inan amount of at least 4.2, for example in an amount of at least 4.4 mol% based on the P1. Preferably the isophthalic acid used for thepreparation of polyester resin P1 is in an amount of at most 6.5, morepreferably in an amount of at most 6.2, even more preferably in anamount of at most 6, most preferably in an amount of at most 5.8,especially in an amount of at most 5.5, more especially in an amount ofat most 5.2, most especially in an amount of at most 5, for example inan amount of at most 4.8 mol % based on the P1.

The terephthalic acid used for the preparation of polyester resin P1 isin an amount of at least 39 and of at most 48 mol %. Preferably theterephthalic acid used for the preparation of polyester resin P1 is inan amount of at least 39.5, more preferably in an amount of at least 40,even more preferably in an amount of at least 40.5, most preferably inan amount of at least 41, especially in an amount of at least 42 mol %based on the P1. Preferably the terephthalic acid used for thepreparation of polyester resin P1 is in an amount of at most 47, morepreferably in an amount of at most 46, even more preferably in an amountof at most 45.5, most preferably in an amount of at most 45.2,especially in an amount of at most 44.8, more especially in an amount ofat most 44.6, even more especially in an amount of at most 44.5 mol %based on the P1.

The adipic acid used for the preparation of polyester resin P1 is in anamount of at least 0.01 and of at most 10 mol %. Preferably the adipicacid used for the preparation of polyester resin P1 is in an amount ofat least 0.5, more preferably in an amount of at least 1, even morepreferably in an amount of at least 1.5, most preferably in an amount ofat least 2, especially in an amount of at least 2.5, more especially inan amount of at least 2.8, even more especially in an amount of at least3, most especially in an amount of at least 3.2, for example in anamount of at least 3.3, for example in an amount of at least 3.4 mol %based on the P1. Preferably, the adipic acid used for the preparation ofpolyester resin P1 is in an amount of at most 9, more preferably in anamount of at most 8, even more preferably in an amount of at most 7,most preferably in an amount of at most 6, especially in an amount of atmost 5.5, more especially in an amount of at most 5, most especially inan amount of at most 4.5, for example in an amount of at most 4, forexample of at most 3.9 mol % based on the P1.

Preferably, the at least trifunctional monomer used for the preparationof polyester resin P1 is in an amount of at least 0.01 and of at most 5mol % based on the P1. Preferably the polycarboxylic acid used for thepreparation of polyester resin P1 is in an amount of at least 0.02, morepreferably in an amount of at least 0.03, even more preferably in anamount of at least 0.04, most preferably in an amount of at least 0.045,especially in an amount of at least 0.05 mol % based on the P1.Preferably, the at least trifunctional monomer used for the preparationof polyester resin P1 is in an amount of at most 5, more preferably inan amount of at most 4, even more preferably in an amount of at most3.5, most preferably in an amount of at most 3.2, especially in anamount of at most 3, more especially in an amount of at most 2.9, evenmore especially in an amount of at most 2.8, most especially in anamount of at most 2.7, for example in an amount of at most 2.6, forexample in an amount of at most 2.5, for example in an amount of at most2.4 mol % based on the P1. Examples of an at least trifunctional monomerare trimethylolpropane, pentaerythritol, glycerol, dipentaerythritol,trimethylolethane. Preferably, the at least trifunctional monomer isselected from the group consisting of trimethylolethane,trimethylolpropane and glycerol. Preferably the at least trifunctionalmonomer is a triol, preferably the at least trifunctional monomer istrimethylolpropane.

Apart from neopentyl glycol and ethylene glycol, other diols that can beused for the preparation of the polyester resin P1 include but are notlimited to: diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, 1,3-butylethyl propanediol,2-butyl-2-ethyl-1,3-propanediol (BEPD), 2-methyl-1,3-propanediol (MPdiol), 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol,1,3-isobutanediol, 1,2-isobutanediol, 2,3-butanediol, 2-butenediol(1,4),2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclopentanediol,1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,6-hexanediol,1,4-dimethoxy cylcohexane, 1,2-cyclohexanediol, 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,4,4′-methylene-bis(cyclohexanol), 4,4′-isopropylidene-bis(cyclohexanol),(hydrogenated bisphenol A) 1,4-bis(hyd roxymethyl)cyclohexane,1,3-bis(hydroxyethyl) cyclohexane, 1,3-bis(hydroxypropyl) cyclohexane,1,3-bis(hydroxyisopropyl) cyclohexane, dodecanediol, xylene glycol,bisphenol A/propylene oxide adducts, hydroquinone/propylene oxideadducts, and hydroquinone/ethylene oxide adducts.

Apart from isophthalic acid, terephthalic acid and adipic acid otherdiacids can be used for the preparation of the polyester resin P1include but are not limited to: 2,6-naphtalene dicarboxylic acid,4,4′-oxybisbenzoic acid, tetrahydrophthalic anhydride,cyclohexanedicarboxylic acid, succinic acid, sebacid acid, phthalicanhydride, maleic anhydride, fumaric acid, itaconic acid.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section6 can be combined with each other.

7. Thermosetting Powder Coating Composition A1 (PCC A1)

The PCC A1 is as described in the entire application and as defined bythe claims.

The PCC A1 is a one component thermosetting powder coating composition.

The PCC A1 can be a heat-curable and/or radiation curable thermosettingpowder coating composition; preferably the PCC A1 is a heat-curablethermosetting powder coating composition.

The PCC A1 can be amorphous or crystalline; preferably the PCC A1 isamorphous.

The thermosetting powder coating composition A1 (PCC A1) comprises abinder K1 in an amount of at least 10 and of at most 100 pph PCC A1,said binder K1 comprising a polyester resin P1 and a crosslinker X1.

Preferably the PCC Al comprises a binder K1 in an amount of at least 15,more preferably of at least 20, even more preferably of at least 30,most preferably of at least 35, especially of at least 40, moreespecially of at least 45, even more especially of at least 50, mostespecially of at least 60, for example of at least 70, for example of atleast 75, for example of at least 80, for example of at least 85, forexample of at least 90, for example of at least 92, for example of atleast 94, for example of at least 96, for example of at least 97, forexample of at least 98, for example of at least 99 pph PCCA1. Preferablythe PCC A1 comprises a binder K1 in an amount of at most 99, morepreferably of at most 98, even more preferably of at most 97, mostpreferably of at most 96, especially of at most 94, more especially ofat most 92, even more especially of at most 90, most especially of atmost 85, for example of at most 80, for example of at most 75, forexample of at most 70, for example of at most 60, for example of at most50, for example of at most 45, for example of at most 40, for example ofat most 35, for example of at most 30, for example of at most 20, forexample of at most 15 pph PCCA1.

The binder K1 comprises a polyester resin P1 in an amount of at least 10and at most 99 pph binder K1. Preferably, the binder K1 comprises a P1in an amount of at least 15, more preferably in an amount of at least20, even more preferably in an amount of at least 25, most preferably ofat least 30, especially in an amount of at least 35, more especially inan amount of at least 40, even more especially in an amount of at least45 most especially in an amount of at least 50 pph binder K1.Preferably, the binder K1 comprises a P1 in an amount of at most 98,more preferably in an amount of at most 97, even more preferably in anamount of at most 95, most preferably of at most 93, especially in anamount of at most 92, more especially in an amount of at most 90, evenmore especially in an amount of at most 85, most especially in an amountof at most 80, for example in an amount of at most 75, for example in anamount of at most 70, for example in an amount of at most 65, forexample in an amount of at most 60, for example in an amount of at most55, for example in an amount of at most 50 pph binder K1.

The binder K1 comprises a crosslinker X1 in an amount of at least 1 andat most 90 pph binder. Preferably, the binder K1 comprises a X1 in anamount of at least 2, more preferably in an amount of at least 3, evenmore preferably in an amount of at least 5, most preferably of at least7, especially in an amount of at least 6, more especially in an amountof at least 8, even more especially in an amount of at least 9, mostespecially in an amount of at least 10, for example in an amount of atleast 11, for example in an amount of at least 12, for example in anamount of at least 13, for example in an amount of at least 14, forexample in an amount of at least 15, for example in an amount of atleast 20, for example in an amount of at least 25, for example in anamount of at least 30, for example in an amount of at least 35, forexample in an amount of at least 40, for example in an amount of atleast 45, for example in an amount of at least 50 pph binder K1.Preferably, the binder K1 comprises a X1 in an amount of at most 85,more preferably in an amount of at most 80, even more preferably in anamount of at most 75, most preferably of at most 70, especially in anamount of at most 65, more especially in an amount of at most 60, evenmore especially in an amount of at most 55, most especially in an amountof at most 50, for example in an amount of at most 45, for example in anamount of at most 40, for example in an amount of at most 35, forexample in an amount of at most 30, for example in an amount of at most25, for example in an amount of at most 20, for example in an amount ofat most 18, for example in an amount of at most 16, for example in anamount of at most 15, for example in an amount of at most 14, forexample in an amount of at most 13, for example in an amount of at most12 for example in an amount of at most 10, for example in an amount ofat most 9, for example in an amount of at most 8, for example in anamount of at most 7 for example in an amount of at most 5 for example inan amount of at most 3, for example in an amount of at most 2 forexample in an amount of at most 1 pph binder K1.

Preferably, the crosslinker X1 is selected from the group consisting ofBHA compounds, epoxy compounds and mixtures thereof; more preferably thecrosslinker X1 is selected from the group consisting of BHA compoundsand epoxy compounds; even more preferably the crosslinker X1 is selectedfrom the group consisting of BHA compounds or equally the crosslinker X1is a BHA compound.

Preferably the BHA compound has at least 3 β-hydroxyalkylamide groups,even more preferably the BHA compound has at least 4 β-hydroxyalkylamidegroups, most preferably the BHA compound has at least 2 and at most 4β-hydroxyalkylamide groups, especially the BHA compound has at least 3and at most 4 β-hydroxyalkylamide groups, more especially the BHAcompound has 4 β-hydroxyalkylamide groups.

Some BHA compounds are disclosed in U.S. Pat. No. 4,727,111, U.S. Pat.No. 4,788,255, U.S. Pat. No. 4,076,917, EP 322834 and EP 473380.

Suitable examples of commercially available BHA compounds are forexample N,N,N′,N′-tetrakis-(2-hydroxyethyl)-adipamide (Primid® XL-552)and N,N,N′,N′-tetrakis-(2-hydroxypropyl)-adipamide (Primid® QM 1260)available from EMS Chemie AG. Primid® XL-552 is an example of a BHAcompound having 4 β-hydroxyalkylamide groups.

If the crosslinker X1 is a BHA compound, then the binder K1 comprises aBHA compound preferably in an amount of at least 1, more preferably inan amount of at least 2 pph binder K1. If the crosslinker X1 is a BHAcompound, then the binder K1 comprises a BHA compound preferably in anamount of at most 25, more preferably in an amount of at most 20, evenmore preferably in an amount of at most 15, most preferably in an amountof at most 13, especially in an amount of at most 10, more especially inan amount of at most 9, even more especially in an amount of at most 8,most especially in an amount of at most 7 pph binder K1.

If the crosslinker X1 is a BHA compound, then the binder K1 comprises apolyester resin P1 preferably in an amount of at least 75, morepreferably in an amount of at least 80, even more preferably in anamount of at least 85, most preferably in an amount of at least 87,especially in an amount of at least 90, more especially in an amount ofat least 91, even more especially in an amount of at least 92 mostespecially in an amount of at least 93 pph binder K1. If the crosslinkerX1 is a

BHA compound, then the binder K1 comprises a polyester resin P1preferably in an amount of at most 99, more preferably in an amount ofat most 98 pph binder K1.

Suitable examples of epoxy compounds include bisphenol-A resins,bisphenol-F epoxy resins, glycidylesters, triglycidylisocyanurates andcombinations thereof. It is preferred to use a an epoxy compound chosenfrom the group consisting of bisphenol-A resins, bisphenol-F epoxyresins, glycidylesters and combinations thereof. More preferably, theepoxy compound is chosen from the group consisting of bisphenol-Aresins, glycidylesters and combinations thereof. Suitable examples ofcommercially available bisphenol-A epoxy resins include Araldite®GT-7004 (Huntsman), Epikote® 1002 (Shell) and DER 662®, DER 663® and DER664® (Dow). Suitable examples of commercially available glycidylestersinclude Araldite®PT910 and Araldite®PT912. Examples oftriglycidylisocyanurates include TGIC (triglycidylisocyanurate), whichis commercially available as Araldite®PT810. Preferably, the epoxycompound is selected from the group consisting of bisphenol-A epoxyresins, triglycidylisocyanurates, and mixtures thereof; more preferablythe epoxy compound is selected from the group consisting of bisphenol-Aepoxy resins, and triglycidylisocyanurates, even more preferably theepoxy compound is a bisphenol-A epoxy resin.

The epoxy compounds can vary considerably in molecular weight. This ismost often expressed as the epoxy equivalent weight (EEW). The epoxyequivalent weight is the weight of an epoxy compound containing exactlyone mole of epoxy groups, expressed in g/mol. Preferably the EEW rangesfrom 100 to 1500, more preferably from 150 to 1200, even more preferablyfrom 200 to 900 and most preferably from 400 to 850 g/mol. If thecrosslinker X1 is an epoxy compound, then the binder K1 comprises anepoxy compound preferably in an amount of at least 2, more preferably inan amount of at least 3, even more preferably in an amount of at least4, most preferably in an amount of at least 5, especially in an amountof at least 6, more especially in an amount of at least 7, even moreespecially in an amount of at least 8, most especially in an amount ofat least 9, for example in an amount of at least 10, for example in anamount of at least 11, for example in an amount of at least 12, forexample in an amount of at least 13, for example in an amount of atleast 14 pph binder K1. If the crosslinker X1 is an epoxy compound, thenthe binder K1 comprises an epoxy compound preferably in an amount of atmost 70, more preferably in an amount of at most 65, even morepreferably in an amount of at most 60, most preferably in an amount ofat most 55, especially in an amount of at most 50, more especially in anamount of at most 45, most especially in an amount of at most 40, forexample of at most 35, for example of at most 30, for example of at most25, for example of at most 20 pph binder K1.

If the crosslinker X1 is an epoxy compound, then the binder K1 comprisesa polyester resin P1 preferably in an amount of at least 40, morepreferably in an amount of at least 45, even more preferably in anamount of at least 50, most preferably in an amount of at least 55,especially in an amount of at least 60 pph binder K1. If the crosslinkerX1 is an epoxy compound, then the binder K1 comprises a polyester resinP1 preferably in an amount of at most 98, more preferably in an amountof at most 97, even more preferably in an amount of at most 96, mostpreferably in an amount of at most 95, especially in an amount of atmost 94, more especially in an amount of at most 93, even moreespecially in an amount of at most 92, most especially in an amount ofat most 91, for example in an amount of at most 90, for example in anamount of at most 89, for example in an amount of at most 88, forexample in an amount of at most 87, for example in an amount of at most86, for example in an amount of at most 80, for example in an amount ofat most 75, for example in an amount of at most 70 pph binder K1.

If the crosslinker X1 is an epoxy compound, preferably the PCC A1comprises a catalyst to promote the crosslinking reaction of thecrosslinker X1 with the polyester P1. Suitable catalysts include aminecontaining compounds, such as tertiary amines, phosphines, imidazoles,quaternary ammonium salts, phosphonium salts, metal salts. Specificsamples of these catalysts are tetrabutylammonium and choline chloride.These catalysts may be used either alone or in combination.

The glass transition temperature (T_(g)) of the PCC Al is preferably atleast 23 more preferably at least 25, even more preferably at least 35,most preferably at least 40, especially at least 45° C. The glasstransition temperature (T_(g)) of the PCC A1 is preferably at most 100°C., more preferably at most 90° C., even more preferably at most 80° C.,most preferably at the most 70° C.

In case in which the PCC A1 has a T_(m), the T_(m) is preferably atleast 23, more preferably at least 25, even more preferably at least 30,most preferably at least 40, especially at least 45, most preferably atleast 50° C. The T_(m) of the PCC A1 is preferably at most 180° C., morepreferably at most 160° C., even more preferably at most 150, mostpreferably at most 140° C.

As is apparent to the skilled person, besides a polyester resin P1, alsoother resins different than polyester resins P1, for example othercarboxylic acid functional polyester resins different than polyesterresin P1, may be present in the binder K1; said resins different thanpolyester resins P1 can be amorphous or crystalline, preferably saidresins are amorphous. Preferably, the amount of a polyester resin P1 inthe binder K1 is at least 90, preferably at least 93, more preferably atleast 95, even more preferably at least 97, most preferably at least 98,especially at least 99 and more especially 100% w/w based on totalamount of resins present in the binder K1. Preferably, the binder K1comprises —apart from a crosslinker X1—, only a polyester resin P1, as acarboxylic acid functional resin, because this offers simplicity informulating.

It is advantageous to use only a polyester resin P1 in the PCC A1 as theuse of only one resin as opposed to a mixture of resins in the PCC A1 isless laborious and economically more attractive.

The PCC A1 may further comprise waxes, pigments, fillers and/or theusual (processing) additives, for example degassing agents, smoothness,appearance enhancing agents or (light) stabilizers. The pigments may beinorganic or organic. Suitable inorganic pigments include for example,titanium dioxide, zinc sulphide, zinc phosphate, mica, iron oxide and/or chromium oxide. Suitable organic pigments include for example azocompounds. Suitable fillers include for example metal oxides, silicates,carbonates and sulphates. Suitable stabilizers include for exampleprimary and/or secondary antioxidants and UV stabilizers for examplequinones, (sterically hindered) phenolic compounds, phosphonites,phosphites, thioethers and HALS (hindered amine light stabilizers).Examples of suitable degassing agents include cyclohexane dimethanolbisbenzoate, benzoin and benzoin derivatives such as for example thosedescribed in WO2/50194. Other additives, such as additives for improvingtribo-chargeability may also be added. Some of these additives may beadded after the polyester resin P1 is prepared in a chemical reactor butbefore the polyester resin P1 is discharged from the chemical reactor.Alternatively, some of these additives may be added in the premix of thethermosetting powder coating composition as described above or in theextruder for instance by liquid injection.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section7 can be combined with each other.

8. Process for Making the PCC A1

The PCC A1 may be prepared by mixing the separately weighed-outcomponents in a mixer, heat the obtained premix, for example in akneader, preferably in an extruder to obtain an extrudate, cool down theobtained extrudate until it solidifies and grind it into granules orflakes that are further ground to reduce the particle size followed byappropriate classification to obtain a thermosetting powder coatingcomposition of the right particle size.

Alternatively, the PCC A may be prepared by mixing the separatelyweighed-out crosslinker X1 with polyester resin P1 to form a premix,heat the obtained premix, for example in a kneader, preferably in anextruder to obtain an extrudate, cool down the obtained extrudate untilit solidifies and grind it into granules or flakes that are furtherground to reduce the particle size. Subsequently, mixing the rest of theseparately weighed-out components and the extrudate of the crosslinkerX1 with the polyester resin P1 to form another premix, heat the thusobtained premix, for example in a kneader, preferably in an extruder toobtain an extrudate, cool down the obtained extrudate until itsolidifies and grind it into granules or flakes that are further groundto reduce the particle size followed by appropriate classification toobtain a thermosetting powder coating composition of the right particlesize.

Preferably, the PCC A1 is prepared by a process comprising the steps of:

-   a. mixing the components of the PCC A1 to obtain a premix;-   b. heating the premix, preferably in an extruder, to obtain an    extrudate;-   c. cooling down the extrudate to obtain a solidified extrudate; and-   d. grinding the solidified extrudate into smaller particles to    obtain the PCC A1.

If the premix is heated in an extruder or mixer/kneader, it is preferredto use a temperature control in order to avoid too high temperaturesthat could lead to curing of the PCC A1 in the extruder. The temperatureshould be set so that a good mixing is ensured bymelting/kneading/mixing of all components to get a homogeneous mass.

Preferably, the PCC A1 is prepared by a process comprising the steps of:

-   a. mixing the crosslinker X1 with the polyester resin P1 to obtain a    premix 1;-   b. heating the premix 1, preferably in an extruder, to obtain an    extrudate of the crosslinker X1 with the polyester resin P1, namely    extrudate 1;-   c. cooling down the extrudate 1 to obtain a solidified extrudate 1;    and-   d. grinding the solidified extrudate 1 into smaller particles to    obtain a mixture of the crosslinker X1 with the polyester resin P1,    namely mixture 1; and-   e. mixing the rest of the components of the PCC Al with the mixture    1, to obtain a premix 2;-   f. heating the premix 2, preferably in an extruder, to obtain an    extrudate 2;-   g. cooling down the extrudate 2 to obtain a solidified extrudate 2;    and-   h. grinding the solidified extrudate 2 into smaller particles to    obtain the PCC A1.

If the premix 1 and/or 2 is/are heated in an extruder or mixer/kneader,it is preferred to use a temperature control in order to avoid too hightemperatures that could lead to curing of the PCC A1 in the extruder.The temperature should be set so that a good mixing is ensured bymelting/kneading/mixing of all components to get a homogeneous mass.

The PCC A1 may be applied to an article using the techniques known tothe person skilled in the art, for example using electrostatic spray orelectrostatic fluidized bed or flame spray.

The PCC A1 may be partially or fully cured via heating and/or radiation.Preferably the PCC A1 is partially or fully cured via heating.

In case of heating the PCC A1 in order to cure it, the heating of thePCC A1 can be carried out at a temperature and for a time suitable tocure the PCC A1.

Heating of the PCC A1 may be done using conventional methods, such aswith a convection oven and/or with an (N)IR lamp and/or infrared laserand/or microwave equipment may be used to heat the PCC A1.

The temperature, at which the PCC A1 is cured, is preferably in therange of 120 to 225° C., more preferably from 130 to 200° C., even morepreferably from 130 to 190° C., most preferably from 130 to 180° C.,especially from 130 to 170° C., more especially from 130 to 160° C.Preferably, the temperature at which the PCC A1 is cured is preferablyat most 225, more preferably at most 200, even more preferably at most190, most preferably at most 180, most preferably at most 170,especially at most 160, more especially at most 150° C. Preferably, thetemperature at which the thermosetting powder coating compositions ofthe invention are cured, is preferably at least 120, more preferably atleast 130, even more preferably at least 135, most preferably at least140, most preferably at least 145, especially at least 150, moreespecially at least 155° C.

Preferably the curing time of the PCC A1 is at most 60, more preferablyis at most 45, even more preferably is at most 30, most preferably is atmost 20, especially is at most 15, more especially is at most 12, evenmore especially is at most 10, most especially is at most 5 minutes.

Preferably the PCC A1 is cured at a temperature in the range of 130-170°C. for a time in the range of 5-30 minutes.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section8 can be combined with each other.

9. Thermosetting Powder Coating Composition B (PCC B)

The PCC B is as described in the entire application and as defined bythe claims.

The PCC B can be a heat-curable and/or radiation curable thermosettingpowder coating composition; preferably the PCC B is a heat-curablethermosetting powder coating composition.

The PCC B is a two component thermosetting powder coating composition.

The PCC B can be amorphous or crystalline; preferably the PCC B isamorphous.

The PCC B comprises a physical mixture of two different, separate anddistinct thermosetting powder coating compositions A (PCC A) and A1 (PCCA1), wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein.

Preferably the PCC B comprises a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and A1 (PCC A1), wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein. and wherein the crosslinkers X and X1 are each selected from    the group consisting of BHA compounds, epoxy compounds and mixtures    thereof.

Preferably the PCC B comprises a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and A1 (PCC A1), wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein. and wherein the crosslinkers X and X1 are each a BHA    compound.

Preferably the PCC B comprises a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and A1 (PCC A1), wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein. and wherein the crosslinkers X and X1 are each the same BHA    compound.

Preferably the PCC B comprises a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and A1 (PCC A1), wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein. and wherein the crosslinkers X and X1 are each an epoxy    compound.

Preferably the PCC B comprises a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and A1 (PCC A1), wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein. and wherein the crosslinkers X and X1 are each the same    epoxy compound.

Preferably, the PCC B comprises a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and A1 (PCC A1), wherein the weight ratio R=weight PCC N weight PCCA1, is at least 0.2 and at most 8 and the total weight of the mixture ofPCC A and PCC A1 in PCC B, is at least 10% w/w based on the total weightof PCC B, and wherein,

-   PCC A is as described in the entire application and as claimed    herein; and-   PCC A1 is as described in the entire application and as claimed    herein.

More particularly, the thermosetting powder coating composition B (PCCB), comprises a physical mixture of two different, separate and distinctthermosetting powder coating compositions A (PCC A) and A1 (PCC A1),wherein PCC A is as described herein and as defined by the claims andwherein the total amount of PCC A and PCC A1 in PCC B, is at least 10pph PCC B, and wherein the weight ratio R=weight PCC N weight PCC A1, isat least 0.2 and at most 8,

and wherein

PCC A1 comprises a binder K1, said binder K1 comprising

-   -   a crosslinker X1 in an amount of at least 1 and of at most 90        pph binder K1; and    -   a branched carboxylic acid functional polyester resin P1 in an        amount of at least 10 and of at most 99 pph binder K1, said        polyester resin P1 having:    -   a. a T_(g) of at least 40° C. as measured by Differential        Scanning calorimetry (DSC) at a heating rate of 5° C./min; and    -   b. an acid value (AV) of at least 19 and of at most 35 mg KOH/g        P1; and    -   c. a hydroxyl value of at most 7 mg KOH/g P1; and    -   d. a functionality of at least 2.1 and of at most 3; and    -   said polyester resin P1 being the reaction product of at least:        -   i) neopentyl glycol in an amount of at least 25 and of at            most 50 mol %; and        -   ii) ethylene glycol in an amount of at least 2.5 and of at            most 20 mol %; and        -   iii) a C₆ diol in an amount of at least 1.1 and of at most            4.9 mol %; and        -   iv) isophthalic acid in an amount of at least 0 and of a            most 6.5 mol %; and        -   v) terephthalic acid in an amount of at least 39 and of at            most 48 mol %; and        -   vi) adipic acid in an amount of at least 1 and of at most 10            mol %; and        -   vii) an at least trifunctional monomer in an amount of at            least 0.001 and of at most 3 mol %; and            -   wherein the mol % is based on the polyester resin P1,            -   and wherein the total amount of monomers used for the                preparation of the polyester resin P1 is 100 mol %.

Preferably R is at least 0.2, more especially at least 0.3, mostespecially at least 0.4, for example at least 0.5, for example at least0.6, for example at least 0.7, for example at least 0.8, for example atleast 0.9, for example at least 0.95, for example at least 0.98, forexample at least 0.99. Preferably R is at most 8, more preferably atmost 7.5, even more preferably at most 7, most preferably at most 6.5,especially at most 6, more especially at most 5.5, most especially atmost 5, for example at most 4.5, for example at most 4, for example atmost 3.5, for example at most 3, for example at most 2.5, for example atmost 2, for example at most 1.5, for example at most 1.4, for example atmost 1.3, for example at most 1.2, for example at most 1.1, for exampleat most 1.05, for example at most 1.02, for example at most 1.01.

Preferably, R is at least 0.2 and at most 8.

Preferably, R is at least 0.3 and at most 3.

Preferably, R is at least 0.4 and at most 2.5.

Preferably, R is at least 0.5 and at most 2.

Preferably, R is at least 0.6 and at most 1.5.

Preferably, R is at least 0.8 and at most 1.3.

Preferably, R is equal to 1 (allowing for rounding errors).

PCC B may further comprise thermosetting powder coating compositionsother than PCC A and PCC A1; preferably PCC B essentially consists ofPCC A and PCC A1; most preferably PCC B consists of PCC A and PCC A1.

The total amount of PCC A and PCC A1 in the PCC B is at least 10,preferably at least 15, more preferably at least 20, even morepreferably at least 25, most preferably at least 30, especially at least35, more especially at least 40, most especially at least 45, forexample at least 50, for example at least 55, for example at least 60,for example at least 65, for example at least 70, for example at least75, for example at least 80, for example at least 85, for example atleast 90, for example at least 95, for example at least 97, for exampleat least 98, for example at least 99, for example at least 99.5, forexample at least 99.9, for example 100 pph PCC B.

The glass transition temperature (T_(g)) of the PCC B is preferably atleast 23, more preferably at least 25, even more preferably at least 35,most preferably at least 40, especially at least 45° C. The glasstransition temperature (T_(g)) of the PCC B is preferably at most 100,more preferably at most 90, even more preferably at most 80, mostpreferably at most 75, especially at most 70° C.

In case in which the PCC B has a T_(m), the T_(m) is preferably at least23, more preferably at least 25, even more preferably at least 30, mostpreferably at least 35, especially at least 40° C. The T_(m) of the PCCB is preferably at most 180, more preferably at most 160, even morepreferably at most 150, most preferably at most 140° C.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section9 can be combined with each other.

10. Process for Making the PCC B

Broadly in accordance with the invention there is provided a process formaking the PCC B comprising the steps of:

-   a. providing a thermosetting powder coating composition A (PPC A) as    disclosed herein and a different, separate, distinct thermosetting    powder coating composition A1 (PPC A1) as disclosed herein; and-   b. physically mixing PCC A with PCC A1, to obtain the PCC B.

Preferably, the process for making the PCC B comprises the steps of:

-   a. providing a thermosetting powder coating composition A (PPC A) as    disclosed herein and a different, separate, distinct thermosetting    powder coating composition A1 (PPC A1) as disclosed herein; and-   b. physically mixing PCC A with PCC Al in a weight ratio R=weight    PCC A/weight PCC A1, that is at least 0.2 and at most 8, to obtain    the PCC B.

Each of PCC A and PCC A1 are prepared separately from each other andeach of them may be prepared as disclosed herein.

Once separately prepared, PCC A and PCC A1 are physically mixed togetherin a weight ratio R that is at least 0.2, more especially at least 0.3,most especially at least 0.4, for example at least 0.5, for example atleast 0.6, for example at least 0.7, for example at least 0.8, forexample at least 0.9, for example at least 0.95, for example at least0.98, for example at least 0.99. Preferably R is at most 8, morepreferably at most 7.5, even more preferably at most 7, most preferablyat most 6.5, especially at most 6, more especially at most 5.5, mostespecially at most 5, for example at most 4.5, for example at most 4,for example at most 3.5, for example at most 3, for example at most 2.5,for example at most 2, for example at most 1.5, for example at most 1.4,for example at most 1.3, for example at most 1.2, for example at most1.1, for example at most 1.05, for example at most 1.02, for example atmost 1.01.

Preferably, R is at least 0.2 and at most 8.

-   Preferably, R is at least 0.4 and at most 2.5.-   Preferably, R is at least 0.5 and at most 2.-   Preferably, R is at least 0.6 and at most 1.5.-   Preferably, R is at least 0.8 and at most 1.3.-   Preferably, R is equal to 1 (allowing for rounding errors).

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section10 can be combined with each other.

11. Cured Thermosetting Powder Coating Composition B and Process forCuring the PCC B and Object Obtainable by and/or Obtained by SaidProcess

Broadly in accordance with the invention there is provided a curedthermosetting powder coating composition B, as the thermosetting powdercoating composition B is described herein. The cured thermosettingpowder coating composition B, is derived upon curing of thethermosetting powder coating composition B, as the thermosetting powdercoating composition B is described herein. Preferably the curedthermosetting powder coating composition B is a powder coating, saidpowder coating can be a primer, top coat or an intermediate coating.

Broadly in accordance with the invention there is provided a process forcuring the PCC B comprising the steps of:

-   i) providing the PCC B; and-   ii) heating and/or radiating the PCC B to partially or fully cure    it.

Preferably step ii) above is carried out via heating.

Broadly in accordance with the invention there is provided a objectobtainable and/or obtained by the aforementioned process for curing thePCC B; said object is the cured thermosetting powder coating compositionB and said cured thermosetting powder coating composition B ispreferably a powder coating, said powder coating can be a primer, topcoat or an intermediate coating.

In case of heating the PCC B in order to cure it, the heating of the PCCB can be carried out at a temperature and for a time suitable to curethe PCC B.

Heating of the PCC B may be done using conventional methods, such aswith a convection oven and/or with an (N)IR lamp and/or infrared laserand/or microwave equipment may be used to heat the PCC B.

The temperature, at which the PCC B is cured, is preferably in the rangeof 120 to 225° C., more preferably from 130 to 200° C., even morepreferably from 130 to 190° C., most preferably from 130 to 180° C.,especially from 130 to 170° C., more especially from 130 to 160° C.Preferably, the temperature at which the PCC B is cured is preferably atmost 225, more preferably at most 200, even more preferably at most 190,most preferably at most 180, most preferably at most 170, especially atmost 160, more especially at most 150° C. Preferably, the temperature atwhich the thermosetting powder coating compositions of the invention arecured, is preferably at least 120, more preferably at least 130, evenmore preferably at least 135, most preferably at least 140, mostpreferably at least 145, especially at least 150, more especially atleast 155° C.

Preferably the curing time of the PCC B is at most 60, more preferablyis at most 45, even more preferably is at most 30, most preferably is atmost 20, especially is at most 15, more especially is at most 12, evenmore especially is at most 10, most especially is at most 5 minutes.

Preferably the PCC B is cured at a temperature in the range of 130-170°C. for a time in the range of 5-30 minutes.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section11 can be combined with each other.

12. Process for Coating an Article With the PCC B and Process forCoating and Curing an Article Having the PCC B Coated and Cured Thereon.

The PCC B may be applied onto an article using the techniques known tothe person skilled in the art, for example using electrostatic spray orelectrostatic fluidized bed or flame spray.

The invention relates also to a process for making an article havingcoated thereon the thermosetting powder coating composition B,comprising the step of applying the thermosetting powder coatingcomposition B to an article to obtain the article having coated thereonthe thermosetting powder coating composition B.

The invention further relates to a process for making an article havingcoated and cured thereon the thermosetting powder coating composition B,comprising the steps of:

-   a. applying the thermosetting powder coating composition B to an    article;-   b. heating and/or radiating the thermosetting powder coating    composition B for enough time (curing time) and at a suitable    temperature (curing temperature) to partially or fully cure the    thermosetting powder coating composition B to obtain the article    having coated and cured thereon a thermosetting powder coating    composition B.

Preferably step b. above is carried out via heating.

Heating of the coated substrate may be done using conventional methods,such as with a convection oven and/or with an (N)IR lamp. Even microwaveequipment may be used to heat the substrate.

The thermosetting powder coating compositions B are not only low bake,but may also be used for fast cure. It is known that thermosettingpowder coating compositions that can be cured at lower temperaturesoffer at the same time the possibility for cure at relatively highertemperatures but for significant shorter times, thus allowing theend-user (powder coaters) to select the optimum cure conditions at will,hence maximizing the process efficiency and the powder coating line'sthroughput.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in section12 can be combined with each other.

13. Other Aspects and Embodiments of the Invention

The invention further relates to a use of:

-   i) a branched carboxylic acid functional polyester resin P as    described herein and as defined by the claims; and/or-   ii) a thermosetting powder coating composition A as described herein    and as defined by the claims; and/or-   iii) a thermosetting powder coating composition B as described    herein and as defined by the claims; and/or-   iv) a cured thermosetting powder coating composition A as described    herein and as defined by the claims; and/or-   v) a cured thermosetting powder coating composition B as described    herein and as defined by the claims; and/or-   vi) an article as described herein and as defined by the claims;-   in powder coatings, powder-in-mould coatings, 3D-printing,    automotive applications (car parts, agricultural machines, composite    structures, ceramic structures, etc.), marine applications (ships,    boats), aerospace applications (planes, helicopters, composite    structures, ceramic structures, etc.), medical applications    (artificial joints, meshes, woven or non-woven sheets, tapes,    ribbons, bands, cables, tube-like products for e.g. ligament    replacement, composite structures, ceramic structures, etc.),    defense applications (ballistic protection, body armour, ballistic    vests, ballistic helmets, ballistic vehicle protection, composite    structures, ceramic structures, etc.), sports/recreational    applications (fencing, skates, skateboarding, snowboarding,    suspension lines on sport parachutes, paragliders, kites, kite lines    for kite sports, climbing equipment, composite structures, ceramic    structures, etc.), architectural applications (windows, doors,    (pseudo-)walls, cables, etc.), bottling applications, household    applications (household appliances, white goods, furniture, computer    housings, etc.), machinery applications (can and bottle handling    machine parts, moving parts on weaving machines, bearings, gears,    composite structures, ceramic structures, computer housings, etc.),    can applications, coil applications, energy applications for e.g.    generators for wind, tide or solar energy, textile applications for    e.g. fabrics, this can be very broad from impregnation technical    textiles to for example complete composites both as coating and as a    binder for composites, and electrical applications (cabinets for    electrical wire or switch boards).

In another aspect the invention relates to a use of a branchedcarboxylic acid functional polyester resin P as described herein and asdefined by the claims for matt powder coatings.

In another aspect the invention relates to a use of a thermosettingpowder coating composition B as described herein and as defined by theclaims for matt powder coatings.

In another aspect the invention relates to a method for obtaining mattpowder coatings using a branched carboxylic acid functional polyesterresin P as described herein and as defined by the claims.

In another aspect the invention relates to a method for obtaining mattpowder coatings using a thermosetting powder coating composition B asdescribed herein and as defined by the claims for matt powder coatings.

In another aspect the invention relates to a use of a thermosettingpowder coating composition A as described herein and as defined by theclaims in 2K thermosetting powder coating compositions.

In another aspect the invention relates to a method for obtaining a 2Kthermosetting powder coating composition comprising a thermosettingpowder coating composition A as described herein and as defined by theclaims.

Yet, another aspect of the invention is a polyester resin P according toExample 1.

Yet, another aspect of the invention is a binder K as described inExamples 17 and 54.

Yet, another aspect of the invention is a thermosetting powder coatingcomposition A according to Examples 17 and 54.

Yet, another aspect of the invention is thermosetting powder coatingcompositions B according to Examples 33-36, 48-51 and 56-57.

Yet, another aspect of the invention is powder coatings derived uponcuring of the thermosetting powder coating compositions B of Examples33-36, 48-51 and 56-57

Many other variations and embodiments of the invention will be apparentto those skilled in the art and such variations are contemplated withinthe scope of the claims.

Any feature, element, component, embodiment, range and especially anypreferred feature, preferred element, preferred embodiment, preferredrange, preferred combination of ranges, preferment described in theentire application can be combined with each other.

Further aspects of the invention and preferred features thereof aregiven in the claims herein.

The invention will now be described in detail with reference to thefollowing non limiting examples which are by way of illustration only.

14. Examples

The invention is explained in more detail with reference to thefollowing non-limiting examples.

In the Examples section:

-   -   the abbreviation P represents a polyester resin according to the        polyester resin P as disclosed herein and as defined by the        claims;    -   the abbreviation P1 represents a polyester resin according to        the polyester resin P1 as disclosed herein and as defined by the        claims;    -   the abbreviation PCC A represents a thermosetting powder coating        composition according to the thermosetting powder coating        composition PCC A as disclosed herein and as defined by the        claims;    -   the abbreviation PCC A1 represents a thermosetting powder        coating composition according to the thermosetting powder        coating composition PCC A1 as disclosed herein and as defined by        the claims;    -   the abbreviation PCC B represents a thermosetting powder coating        composition according to the thermosetting powder coating        composition PCC B as disclosed herein and as defined by the        claims.

In the Examples section:

-   -   the abbreviation CompP represents a polyester resin that is not        according to the polyester resin P as the latter is disclosed        herein and as is defined by the claims;    -   the abbreviation CompP1 represents a polyester resin that is not        according to the polyester resin P1 as the latter is disclosed        herein and as is defined by the claims;    -   the abbreviation CompPCC A represents a thermosetting powder        coating composition that is not according to the thermosetting        powder coating composition PCC A as the latter is disclosed        herein and as defined by the claims;    -   the abbreviation CompPCC A1 represents a thermosetting powder        coating composition that is not according to the thermosetting        powder coating composition PCC A1 as the latter is disclosed        herein and as is defined by the claims;    -   the abbreviation CompPCC B represents a thermosetting powder        coating composition that is not according to the thermosetting        powder coating composition PCC B as the latter is disclosed        herein and as is defined by the claims.

In the Examples the abbreviation “n.m.” denotes “not measured”.

In the numbers shown in the Tables, the decimal sign is denoted by acomma “,”; for any other number shown in the application, the decimalsign is denoted by a point “.”.

14.1 Analytical Methods and Techniques for the Measurement of theProperties of the Polyester Resins

Unless otherwise stated the theoretical number average molecular weight(M_(n)) is defined as follows:

M_(n)=(Σ_(i)N_(i)M_(i))/(Σ_(i)Ni)

-   where N_(i) is the number of molecules of molecular weight M_(i).

In the case of the polyester resins shown in the Examples 1-16, theM_(n) was calculated by multiplying the functionality (f)—as definedherein—with 56110 and dividing the outcome thereof by the sum of thedesired (targeted) acid value (AV) (mg KOH/g polyester resin) and thedesired (targeted) hydroxyl value (OHV) (mg KOH/g polyester resin)according to the equation EQ1.

The “functionality (f)” of the polyester resins shown in the Examples1-16, was calculated according to equation EQ2.

Melt viscosity (herein mentioned as viscosity, in Pa·s) measurementswere carried out at 160° C. on a Brookfield CAP 2000+H Viscometer. Theapplied shear-rate was 21 s⁻¹ and a 19.05 mm spindle (cone spindleCAP-S-05 (19.05 mm, 1.8°) was used.

The acid and hydroxyl values of the polyester resins P, were determinedtitrimetrically according to ISO 2114-2000 and ISO 4629-1978,respectively; in addition the targeted (theoretical) acid and hydroxylvalues of said resins were also reported herein.

The hydroxyl value of the polyester resins P-1, P1-1, P1-2, P1-3 andP1-4 prepared and shown in the Examples section was lower than 5 mgKOH/g polyester resin.

All the polyesters prepared and shown in the Examples section wereamorphous.

14.2 DSC Method for the Measurement of Glass Transition Temperature,Crystallization Temperature, Crystallization Enthalpy, MeltingTemperature and Melting Enthalpy for Polyester Resins and/orThermosetting Powder Coating Compositions (mentioned as “DSC Method”)

The glass transition temperature, crystallization temperature,crystallization enthalpy, melting temperature and melting enthalpy of apolyester resin, was/is measured via Differential Scanning calorimetry(DSC) according to the methodology described in this section, on a TAinstruments DSC Q20 apparatus, in N₂ atmosphere calibrated with indium,within 24 hours from the time of preparation of the polyester resin. Theprocessing of the signal (DSC thermogram, Heat Flow vs. Temperature) wasor is to be carried out using Universal Analysis 2000 software version4.5 a provided by TA instruments, as described herein after. The part ofthe DSC Method referring to the polyester resins is mentioned herein asDSC Method-PR.

The glass transition temperature, crystallization temperature,crystallization enthalpy, melting temperature and melting enthalpy of athermosetting powder coating composition was/is measured viaDifferential Scanning calorimetry (DSC) according to the methodologydescribed in this section, on a TA instruments DSC Q20 apparatus, in N₂atmosphere calibrated with indium, within 24 hours from the time ofpreparation of the polyester resin. The processing of the signal (DSCthermogram, Heat Flow vs. Temperature) was or is to be carried out usingUniversal Analysis 2000 software version 4.5a provided by TAinstruments, as described herein after. The part of the DSC Methodreferring to the thermosetting powder coating compositions is mentionedherein as DSC Method-TPCC.

Each one of the glass transition temperature of the polyester resin (seeDSC Method-PR) and the glass transition temperature of the thermosettingpowder coating composition (DSC Method-TPCC) was/is the inflection pointtemperature of the temperature range over which the glass transitiontook place, said inflection point temperature was the point on thethermal curve corresponding to the peak of the first derivative (withrespect to time) of the parent thermal curve. This point corresponds tothe inflection point of the parent thermal curve, as defined in §3.2.1.3in ASTM E 1356-08.

The T_(m) (in DSC Method-PR and DSC Method-TPCC) is measured as thetemperature recorded at the minimum heat flow of the endothermic signalattributed to the melting of the sample.

The ΔH_(m) (in DSC Method-PR and DSC Method-TPCC) is measured as theintegrated heat flow over the temperature range of the melting.

The T_(c) (in DSC Method-PR and DSC Method-TPCC) is measured as thetemperature recorded at the maximum heat flow of the exothermic signalattributed to the crystallization of the sample.

The ΔH_(c) (in DSC Method-PR and DSC Method-TPCC) is measured as theintegrated heat flow over the temperature range of the crystallization.

14.2.1 Polyester Resins (“DSC Method-PR”)

The glass transition temperature (T_(g) in ° C.) of the polyester resinswas measured as follows: a sample of 10±5 mg of the polyester resin wasweight and placed in the DSC cell. The sample was heated up to 150° C.at a heating rate of 40° C./minute (thermograph A). Once the sample hasreached 150° C., the temperature was maintained at 150° C. for 10minutes. Subsequently, the sample was cooled down to 0° C. at a heatingrate of 30° C. (thermograph B); once the sample has reached 0° C., thetemperature was maintained at 0° C. for 1 minute. Subsequently, thesample was heated up to 100° C. at a heating rate of 5° C./minute(thermograph C). Thermographs A, B and C were processed as the Y axis ofthe thermographs representing the heat flow having exotherm up andendotherm down. Thermograph C was used to measure the glass transitiontemperature (T_(g)) of the polyester resins.

The ΔH_(m), T_(m), ΔH_(c) and T_(c) of a polyester resin are measured asfollows: a sample of 10±5 mg of the crystalline polyester resin isweight and placed in the DSC cell. The sample is equilibrated at 25° C.for 1 minute; Subsequently the sample is heated up to 200° C. at aheating rate of 5° C./minute. Once the sample has reached 200° C., thetemperature was maintained at 200° C. for 1 minute (thermograph A).Subsequently, the sample is cooled down to −50° C. at a cooling rate of5° C./minute (thermograph B); once the sample is reached −50° C., thetemperature is maintained at −50° C. for 1 minute. Subsequently, thesample is heated up to 200° C. at a heating rate of 5° C./minute(thermograph C). Thermographs A, B and C were processed as the Y axis ofthe thermographs representing the heat flow has exotherm up andendotherm down.

-   Thermograph B is used for measuring the ΔH_(c) and T_(c);    thermograph C is used to measure the ΔH_(m) and T_(m).

14.2.2 Thermosetting Powder Coating Compositions (“DSC Method-TPCC”)

The glass transition temperature of the thermosetting powder coatingcompositions (T_(g) in ° C.) is measured 24 h after extrusion asfollows: a sample of 10±5 mg of the thermosetting powder coatingcomposition was weight and placed in the DSC cell. The sample was cooleddown to −20° C. and the temperature was kept at −20° C. for 1 minute;Subsequently the sample was heated up to 200° C. at a heating rate of 5°C./minute (thermograph A). Thermograph A was used for measuring theT_(g PCC).

The ΔH_(m) , T_(m), ΔH_(c) and T_(c) of a thermosetting powder coatingcomposition are measured as follows: a sample of 10±5 mg of thethermosetting powder coating composition is weight and placed in the DSCcell. The sample is equilibrated at 25° C. for 1 minute; Subsequentlythe sample is heated up to 120° C. at a heating rate of 5° C./minute.Once the sample has reached 120° C., the temperature was maintained at120° C. for 1 minute (thermograph A). Subsequently, the sample is cooleddown to −50° C. at a cooling rate of 5° C./minute (thermograph B); oncethe sample is reached −50° C., the temperature is maintained at −50° C.for 1 minute. Subsequently, the sample is heated up to 200° C. at aheating rate of 5° C./minute (thermograph C). Thermographs A, B and Cwere processed as the Y axis of the thermographs representing the heatflow has exotherm up and endotherm down. Thermograph B is used formeasuring the ΔH_(c) and T_(c); thermograph C is used to measure theΔH_(m) and T_(m).

14.3 Measurement and Assessment of Properties of the ThermosettingPowder Coating Compositions and the Powder Coatings Thereof (Table 6)

The physical storage stability (PSS) of the thermosetting powder coatingcompositions of Table 7 was tested according to ISO 8130/ part 8, at 40°C. for a total of 7 weeks. The measurement of the PSS of saidthermosetting powder coating compositions was initiated upon extrusionand cooling down at room temperature for about 3 hours. The greater theextend of agglomeration or sintering the poorer the PSS, thus the lowerits ranking according to the following scale. The extent ofagglomeration was visually assessed and ranked according to thefollowing rating on a 1-10 scale (1 representing the worst PSS and 10the best PSS):

-   10: No change.-   9: No agglomeration, very good fluidity.-   8: No agglomeration, good fluidity.-   7: Very low agglomeration; agglomeration can be dispersed by one    light tap into a fine powder.-   6: Very low agglomeration; agglomeration can be dispersed by several    taps into a fine powder.-   5: Low agglomeration; agglomeration can be dispersed by hand    pressure into a fine powder.-   4: Low agglomeration; agglomeration cannot be dispersed by hand    pressure in a fine powder.-   3: Severe agglomeration into several large lumps, material is    pourable.-   2: Severe agglomeration into several large lumps, material is not    pourable.-   1: product sintered to one lump, volume reduced.

The coating (film) thickness of the powder coatings derived upon heatcuring of the corresponding thermosetting powder coating compositions,was measured with a PosiTector 6000 coating thickness gauge fromDeFelsko Corporation according to EN ISO 2808:2007.

Reverse impact resistance (RIR) [in.-lb (inch-pounds), 1inch/lbs=0.055997 m/kg] was tested according to ASTM D 2794, with a 5/8″ball at 20, 40 and 60 in.-lb and at a film thickness of 50±5 μm onALQ-46 panels on the same day after the curing took place and thecoating was cooled to room temperature. The number of in.-lb mentionedin the row for RIR indicates the maximum in.-lb a powder coatingwithstood when its corresponding thermosetting powder coatingcomposition was cured for 12 minutes at 160° C. A ‘0’ indicates that thecoating did not withstand an impact of 20 in.-lb.

Low bake of a cured thermosetting powder coating composition (or‘thermosetting cured powder coating composition’) is defined herein asthe curing temperature and time condition at which the resulted powdercoating having coating thickness of 50±5 μm, showed no cracks ordelamination after having been subjected to reverse impact resistancewas tested on ALQ-46 panels according to ASTM D 2794 as described above.

Gloss60° of the powder coatings derived upon curing of the correspondingthermosetting powder coating compositions on ALQ-46 panels were measuredaccording to ASTM D523 with a BYK-Gardner GmbH Haze-Gloss meter. Thegloss is reported at angle 60° in gloss units and it was measured at afilm thickness of 60±5 μm on ALQ-46 panels.

14.4 Examples 1-3: Synthesis of Polyester Resins P-1, CompP1-1 andCompP1-2: General

The composition of the polyester resins P-1, CompP1-1 and CompP1-2 asshown in Table 1, refers to a yield of 1,0 Kg of polyester resin.

The polyester resins of Examples P-1, CompP1-1 and CompP1-2 wereprepared via a two phase (or two step) polycondensation reaction. At theend of the first step a hydroxyl functional polyester resin was obtained(mentioned herein as precursor); next the hydroxyl functional polyesterresin was reacted further with excess of carboxylic acid functionalmonomers to obtain the polyester resins P-1, CompP1-1 and CompP1-2.

The polyester resins P-1, CompP-1 and CompP-2 are all carboxylic acidfunctional polyesters and all of them have a hydroxyl value (OHV) lowerthan 7 mg KOH/g polyester resin.

Each of the polyester resins P-1, CompP1-1 and CompP1-2 was solid atroom temperature and at atmospheric pressure.

Each of the polyester resins P-1, CompP1-1 and CompP1-2 was amorphous.

The synthesis of polyester resins CompP1-1 and CompP1-2 was performedanalogously to the synthesis of polyester resin P-1 described hereinafter.

14.4.1 Example 1: Synthesis of Polyester Resin P-1

A reactor vessel fitted with a thermometer, a stirrer and a distillationdevice for the removal of water formed during the synthesis, was filledwith butyl stanoic acid (1 g) (catalyst), neopentyl glycol (288.5 g,2.77 mol), ethylene glycol (89.0 g, 1.43 mol). The vessel was heated upto 150° C. until the mixture was molten. Then terephthalic acid (571.8g, 3.44 mol), adipic acid (46.6 g, 0.35 mol) and trimellitic anhydride(20.0 g, 0.10 mol) were added and under a nitrogen flow the temperaturewas gradually increased to 260° C. while distilling off the reactionwater until the acid value of the precursor of the polyester resin wasbetween 9 and 15 mg KOH/g. The reaction mixture was cooled to 240° C.and vacuum was applied until the precursor of the polyester resinreached the desired acid value (7.0 mg KOH/g); that marked thecompletion of the first step. For the second step the reaction mixturewas cooled to 200° C. and subsequently the trimellitic anhydride (113.9g, 0.59 mol) was added. The temperature was raised to 225° C. and thepolyester resin was stirred for one hour at 225° C. Subsequently thepolyester resin was cooled down to 195° C. (marking the end of thesecond step), prior being discharged onto an aluminum foil that was keptat room temperature.

14.5 Examples 4-16: Synthesis of Polyester Resins P1-1, P1-2, P1-3, P1-4and CompP1-1, CompP1-2, CompP1-3, CompP1-4, CompP1-5, CompP1-6,CompP1-7, CompP1-8, CompP1-9: General

The composition of polyester resins P1-1, P1-2, P1-3, P1-4 and CompP1-1,CompP1-2, CompP1-3, CompP1-4, CompP1-5, CompP1-6, CompP1-7, CompP1-8,CompP1-9 as shown in Tables 2 and 3, refer to a yield of 1,0 Kg ofpolyester resin.

The polyester resins P1-1, P1-2, P1-3, P1-4 and CompP1-1, CompP1-2,CompP1-3, CompP1-4, CompP1-5, CompP1-6, CompP1-7, CompP1-8, CompP1-9were prepared via a two phase (or two step) polycondensation reaction.At the end of the first step a hydroxyl functional polyester resin(mentioned herein as precursor) was obtained; next the hydroxylfunctional polyester resin was reacted further with excess of carboxylicacid functional monomers to obtain the branched amorphous carboxylicacid functional polyesters of the Examples P1-1, P1-2, P1-3, P1-4 andCompP1-1, CompP1-2, CompP1-3, CompP1-4, CompP1-5, CompP1-6, CompP1-7,CompP1-8, CompP1-9.

The polyester resins of Tables 2 and 3 were all carboxylic acidfunctional polyesters and all of them had a hydroxyl value (OHV) lowerthan 5 mg KOH/g polyester resin.

Each of the polyester resins of Tables 2 and 3 was solid at roomtemperature and at atmospheric pressure.

Each of the polyester resins shown in Tables 2 and 3 was amorphous.

The synthesis of the polyester resins P1-2, P1-3, P1-4 and CompP1-1,CompP1-2, CompP1-3, CompP1-4, CompP1-5, CompP1-6, CompP1-7, CompP1-8,CompP1-9 was performed analogously to the synthesis of polyester resinP1-1 described herein after.

14.5.1 Example 4: Synthesis of the Polyester Resin P1-1

A reactor vessel fitted with a thermometer, a stirrer and a distillationdevice for the removal of water formed during the synthesis, was filledwith butyl stannoic acid (1 g) (catalyst), neopentyl glycol (314.8 g,3.02 mol), trimethylol propane (8.03 g, 0.06 mol), ethylene glycol (55.0g, 0.89 mol), 1,6-hexanediol (31.2 g, 0.26 mol). The vessel was heatedup to 150° C. until the mixture was molten. Then terephthalic acid(620.2 g, 3.73 mol) and isophthalic acid (23.1 g, 0.14 mol) were addedand under a nitrogen flow the temperature was gradually increased to260° C. while distilling off the reaction water, until the reactionmixture was clear and the acid value of the precursor of the polyesterresin was between 5 and 15 mg KOH/g; that marked the completion of thefirst step. For the second step the reaction mixture was cooled to 200°C. and subsequently the adipic acid (45.8 g, 0.31 mol) and isophtalicacid (44.0 g, 0.26 mol) were added. The temperature was raised to 250°C. while distilling off water; subsequently vacuum was applied until thepolyester resin reached the desired acid value range (25.0 mg KOH/gpolyester resin). Subsequently, the vacuum was stopped and the polyesterresin was cooled down to 195° C. (marking the end of the second step),prior being discharged onto an aluminum foil that was kept at roomtemperature.

14.6 Preparation of Thermosetting Powder Coating Compositions of Table4: General Procedure

The components used to prepare the thermosetting powder coatingcompositions PCC A-1, CompPCC A-1, CompPCC A-2 are described in Table 4;Primid® XL-552 (T_(m)=120-124° C., hydroxyl value 620-700 mg KOH/gPrimid® XL-552) is a BHA-compound supplied from EMS Chemie and it wasused as a crosslinker.

The brown mixture mentioned in Table 4 consisted of 0.4 g Printex® 300(carbon black from Evonik Degussa GmbH), 1.9 g Bayferrox® red 130M(Pigment red C.I. 101 Fe2O3 from Bayer B. V.), 2.9 g Bayferrox® 920(C.I. pigment yellow 42 FeOOH from Bayer), 2.2 g SICOTAN® Yellow L2010

-   (chromium(III)/antimony(V)/titanium dioxide rutile from BASF), 25.0    g Blanc fixe micro (precipitated bariumsulphate from Sachtleben    Chemie GmbH), 1.5 g Resiflow® PV 5 (flow control agent from    Worlée-Chemie GmbH) and 0.4 g benzoin (degassing agent). The total    amount of the brown mixture used was 34.3 pph binder (=polyester    resin and crosslinker). The total amount of the brown mixture that    is to be used is 34.3 pph binder (=polyester resin and crosslinker)    and the amounts of the individual components of the brown mixture    should also be used in a ratio proportional to the one described in    this paragraph for the brown mixture. The foregoing applies for any    thermosetting powder coating composition (inventive or comparative)    that is formulated with the brown mixture.

The thermosetting powder coating compositions of Table 4 were preparedby mixing their components in a blender and subsequently extruding theobtained mixture in a PRISM TSE16 PC twin screw at 120° C. with a screwspeed of 200 rpm. The extrudate was allowed to cool at room temperatureand it was then chopped into chips. The chips were milled in a RetschZM100 with a 0.5 mm ring sieve at 18000 rpm and then sieved. The sievefraction with particle size below 90 μm was collected.

All the thermosetting powder coating compositions of Table 4 were brown.

14.7 Preparation of Thermosetting Powder Coating Compositions of Table5: General Procedure

The components used to prepare the thermosetting powder coatingcompositions PCC A1-1, PCC A1-2, PCC A1-3, PCC A1-4, CompPCC A1-1,CompPCC A1-2, CompPCC A1-3, CompPCC A1-4, CompPCC A1-5, CompPCC A1-6,CompPCC A1-7, CompPCC A1-8 and CompPCC A1-9,are described in Table 5;Primid® XL-552 (T_(m)=120-124° C., hydroxyl value 620-700 mg KOH/gPrimid® XL-552) is a BHA-compound supplied from EMS Chemie and it wasused as a crosslinker.

The brown mixture mentioned in Table 5 was the same as the one used forthe preparation of the thermosetting powder coating compositions ofTable 4 and the total amount of the brown mixture used was 34.3 pphbinder (=polyester resin and crosslinker).

The thermosetting powder coating compositions of Table 5 were preparedby mixing their components in a blender and subsequently extruding theobtained mixture in a PRISM TSE16 PC twin screw at 120° C. with a screwspeed of 200 rpm. The extrudate was allowed to cool at room temperatureand it was then chopped into chips. The chips were milled in a RetschZM100 with a 0.5 mm ring sieve at 18000 rpm and then sieved. The sievefraction with particle size below 90 μm was collected.

All the thermosetting powder coating compositions of Table 5 were brown.

14.8 Preparation of Thermosetting Powder Coating Compositions of Tables6-7: General Procedure

The thermosetting powder coating compositions of Tables 6 and 7 wereprepared by physical mixing carried out by mechanical mixing/blending oftheir components; the components of each of the thermosetting powdercoating compositions of Tables 6 and 7 were the two different, separateand distinct thermosetting powder coating compositions of Tables 4 and5; each of the thermosetting powder coating compositions of Table 6 wereprepared by physically mixing in a blender 100 g of each of theircomponents. For example PCC B-1 was prepared by physically mixing 100 gof PCC A-1 with 100 g of PCC A1-1. All the thermosetting powder coatingcompositions of Table 6 were brown.

Each of the thermosetting powder coating compositions of Table 7—apartfrom Example 33 which was prepared as those examples in Table 6—wereprepared by physically mixing in a blender amounts such amounts of eachof their components so that to obtain thermosetting powder coatingcompositions B having different weight ratios R. For example PCC B8 wasprepared by physically mixing 120 g of PCC A-1 with 80 g of PCC A1-1(R=1.50). All the thermosetting powder coating compositions of Table 7were brown.

Once prepared the thermosetting powder coating compositions of Table 6,were electrostatically sprayed (corona, 60 kV) onto 0.8 mm thickchromate aluminium Q-panels (type: ALQ-46) to a coating thickness tosuit each test mentioned herein and cured at 160° C. for 12 minutes inan air-circulation oven (Heraeus Instruments UT6120) at atmosphericpressure to provide brown powder coatings.

14.9 Preparation of Thermosetting Powder Coating Compositions of Table8: General Procedure

The components used to prepare the thermosetting powder coatingcompositions PCC A-2, and PCC A1-5 are described in Table 8; Araldite®GT-7004 (softening point=95-101° C., epoxy equivalent 714-752g/equivalent Araldite® GT-7004) is an epoxy compound (epoxy resin)supplied from Huntsman Advanced Materials (Europe) BVBA and it was usedas a crosslinker.

The brown mixture mentioned in Table 8 was the same as the one used forthe preparation of the thermosetting powder coating compositions ofTable 4 wherein each of the individual components of the brown mixturewas used in a ratio proportional to the one described for the brownmixture which was used for the preparation of the of Table 4 and whereinthe total amount of the brown mixture that was used for thethermosetting powder coating compositions of Table 8 was 34.3 pph binder(=polyester resin and crosslinker).

The thermosetting powder coating compositions of Table 8 were preparedby mixing their components in a blender and subsequently extruding theobtained mixture in a PRISM TSE16 PC twin screw at 120° C. with a screwspeed of 200 rpm. The extrudate was allowed to cool at room temperatureand it was then chopped into chips. The chips were milled in a RetschZM100 with a 0.5 mm ring sieve at 18000 rpm and then sieved. The sievefraction with particle size below 90 μm was collected.

All the thermosetting powder coating compositions of Table 8 were brown.

14.10 Preparation of Thermosetting Powder Coating Compositions of Table9: General Procedure

The thermosetting powder coating compositions of Table 9 were preparedby physical mixing carried out by mechanical mixing/blending of theircomponents; the components of each of the thermosetting powder coatingcompositions of Table 9 were the two different, separate and distinctthermosetting powder coating compositions of Table 8; each of thethermosetting powder coating compositions of Table 9 were prepared byphysically mixing in a blender such amounts of each of their componentsso that to obtain thermosetting powder coating compositions B havingdifferent weight ratios R. For example PCC B10 was prepared byphysically mixing 134 g of PCC A-2 with 66 g of PCC A1-5 (R=2.03). Allthe thermosetting powder coating compositions of Table 9 were brown.

Once prepared the thermosetting powder coating compositions of Table 9,were electrostatically sprayed (corona, 60 kV) onto 0.8 mm thickchromate aluminium Q-panels (type: ALQ-46) to a coating thickness tosuit each test mentioned herein and cured at 160° C. for 12 minutes inan air-circulation oven (Heraeus

Instruments UT6120) at atmospheric pressure to provide brown powdercoatings.

The object of the invention was to provide storage stable, low bakethermosetting powder coating compositions that upon curing provide mattpowder coatings having good reverse impact resistance (RIR).

By “low bake thermosetting powder coating compositions” is meant hereinbrown thermosetting powder coating compositions that upon curing at 160°C. for 12 min, provide brown powder coatings having reverse impactresistance (RIR) of 40 in.-lb at a film thickness of 50±5 μm (1μm=1×10⁻⁶ m), as RIR is defined and measured herein.

By “thermosetting powder coating composition having good storagestability” is meant herein that a brown thermosetting powder coatingcomposition has a physical storage stability (PSS) of at least 5, morepreferably of at least 6, even more preferably of at least 7, on a scalefrom 1 (very poor storage stability) up to 10 (excellent storagestability), as the PSS is defined and measured herein.

By “matt powder coatings” or “equally “low gloss powder coatings” ismeant herein a brown powder coating having a thickness of 60±5 μm thatis obtained upon curing at 160° C. for 12 min of a brown thermosettingpowder coating composition, said brown powder coating having a gloss 60°of at most 38, preferably of at most 36, more preferably of at most 35,as gloss 60° is defined and measured herein.

By “powder coating having good reverse impact resistance” is meantherein a brown powder coating having a thickness of 50±5 μm that isobtained upon curing at 160° C. for 12 min of a brown thermosettingpowder coating composition, said brown powder coating is able towithstand at least 40, preferably at least 45, more preferably at least50, even more preferably at least 55, most preferably at least 60 in.-lb(1 inch/lbs=0.055997 m/kg), as the reverse impact resistance (RIR) isdefined and measured herein.

From the results presented in Tables 6, 7 and 9, it becomes clear thatonly thermosetting powder coating compositions B (see Examples 33-36,48-51, 56-57) as described herein and as defined by the claims presenteda unique combination of the aforementioned desirable properties; moreparticularly only the thermosetting powder coating compositions B ofExamples 33-36 48-51, and 56-57 were:

-   -   low bake; and    -   storage stable (PSS in the range of 5-9); and provided upon        curing    -   matt powder coatings (gloss60° in the range of 30-36), having a        reverse impact resistance of 60 in.-lb.

1. A branched carboxylic acid functional polyester resin P, having: a. aT_(g) of at least 40° C. as measured by Differential Scanningcalorimetry (DSC) at a heating rate of 5° C./min; and b. an acid value(AV) of at least 65 and of at most 76.8 mg KOH/g P; and c. a hydroxylvalue of at most 10 mg KOH/g P; and d. a functionality of at least 3.5and of at most 5; and said polyester resin P being the reaction productof at least the following monomers: i) neopentyl glycol in an amount ofat least 19 and of at most 38 mol %; and ii) ethylene glycol in anamount of at least 8 and of at most 21 mol %; and iii) a polyol in anamount of at least 0 and of at most 2 mol %; and iv) isophthalic acid inan amount of at least 0 and of at most 3 mol %; and v) terephthalic acidin an amount of at least 38 and of at most 47 mol %; and vi) adipic acidin an amount of at least 0.01 and of at most 10 mol %; and vii) apolycarboxylic acid, in an amount of at least 6 and of at most 10.2 mol%; and wherein the mol % is based on the polyester resin P and whereinthe total amount of monomers used for the preparation of the polyesterresin P is 100 mol %.
 2. The branched carboxylic acid functionalpolyester resin P according to claim 1, wherein the amount of the polyolis at least 0 and at most 1.4 mol %.
 3. The branched carboxylic acidfunctional polyester resin P according to claim 1, wherein the branchedcarboxylic acid functional polyester resin P has an AV of at least 68 mgKOH/g P.
 4. The branched carboxylic acid functional polyester resin Paccording to claim 1, wherein the neopentyl glycol is in an amount of atmost 36.5 mol %.
 5. The branched carboxylic acid functional polyesterresin P according to claim 1, wherein the polycarboxylic acid is in anamount of at least 6.5 mol %.
 6. A thermosetting powder coatingcomposition A (PCC A) comprising a binder K, said binder K comprising: acrosslinker X in an amount of at least 1 and of at most 90 pph binder K;and a branched carboxylic acid functional polyester resin P as definedin claim 1, in an amount of at least 10 and of at most 99 pph binder K.7. The thermosetting powder coating composition A (PCC A) according toclaim 6, wherein the crosslinker X is selected from the group consistingof epoxy compounds, compounds having at least two β-hydroxyalkylamidegroups (BHA compounds) and mixtures thereof.
 8. The thermosetting powdercoating composition A (PCC A) according to claim 6, wherein thecrosslinker X is a BHA compound.
 9. A thermosetting powder coatingcomposition B (PCC B), comprising a physical mixture of two different,separate and distinct thermosetting powder coating compositions A (PCCA) and Al (PCC Al), wherein PCC A is as defined in claim 6 and whereinthe total amount of PCC A and PCC A1 in PCC B, is at least 10 pph PCC B,and wherein the weight ratio R=weight PCC A/weight PCC A1, is at least0.2 and at most 8, and wherein PCC A1 comprises a binder K1, said binderK1 comprising a crosslinker X1 in an amount of at least 1 and of at most90 pph binder K1; and a branched carboxylic acid functional polyesterresin P1 in an amount of at least 10 and of at most 99 pph binder K1,said polyester resin P1 having: a. a T_(g) of at least 40° C. asmeasured by Differential Scanning calorimetry (DSC) at a heating rate of5° C./min; and b. an acid value (AV) of at least 19 and of at most 35 mgKOH/g P1; and c. a hydroxyl value of at most 7 mg KOH/g P1; and d. afunctionality of at least 2.1 and of at most 3; and said polyester resinP1 being the reaction product of at least the following monomers: i)neopentyl glycol in an amount of at least 25 and of at most 50 mol %;and ii) ethylene glycol in an amount of at least 2.5 and of at most 20mol %; and iii) a C₆ diol in an amount of at least 1.1 and of at most4.9 mol %; and iv) isophthalic acid in an amount of at least 0 and of amost 6.5 mol %; and v) terephthalic acid in an amount of at least 39 andof at most 48 mol %; and vi) adipic acid in an amount of at least 1 andof at most 10 mol %; and vii) an at least trifunctional monomer in anamount of at least 0.001 and of at most 3 mol %; and wherein the mol %is based on the polyester resin P1 and wherein the total amount ofmonomers used for the preparation of the polyester resin P1 is 100 mol%.
 10. The thermosetting powder coating composition B according to claim9, wherein the amount of the at least trifunctional monomer is at least0.01 and at most 2.5 mol %.
 11. The thermosetting powder coatingcomposition B according to claim 9, wherein the branched carboxylic acidfunctional polyester resin P1 has an AV of at most 32 mg KOH/g P1. 12.The thermosetting powder coating composition B according to claim 9,wherein the branched carboxylic acid functional polyester resin P1 hasan AV of at least 20 mg KOH/g P1.
 13. The thermosetting powder coatingcomposition B according to claim 9, wherein the branched carboxylic acidfunctional polyester resin P1 has an AV of at least 20 and of at most 28mg KOH/g P1.
 14. The thermosetting powder coating composition Baccording to claim 9, wherein the weight ratio R is at least 0.3 and atmost
 3. 15. The thermosetting powder coating composition B according toclaim 9, wherein the weight ratio R is at least 0.4 and at most 2.5. 16.The thermosetting powder coating composition B according to claim 9,wherein the weight ratio R is at least 0.6 and at most 1.5.
 17. Thethermosetting powder composition B according to claim 9, wherein thecrosslinker X is selected from the group consisting of epoxy compounds,BHA compounds and mixtures thereof and the crosslinker X1 is selectedfrom the group consisting of epoxy compounds, BHA compounds and mixturesthereof.
 18. The thermosetting powder composition B according to claim9, wherein the crosslinker X is a BHA compound and the crosslinker X1 isa BHA compound.
 19. A cured thermosetting powder coating composition A,as the thermosetting powder coating composition A is defined in claim 6.20. The cured thermosetting powder coating composition A according toclaim 19, wherein said cured thermosetting powder coating composition Ais a powder coating.
 21. A cured thermosetting powder coatingcomposition B, as the thermosetting powder coating composition B isdefined in claim
 9. 22. The cured thermosetting powder coatingcomposition B according to claim 21, wherein said cured thermosettingpowder coating composition B is a powder coating.
 23. An article havingcoated thereon either a thermosetting powder coating composition A asdefined in claim 6 or a thermosetting powder coating composition B. 24.An article having coated and cured thereon either a thermosetting powdercoating composition A as defined in claim 6 or a thermosetting powdercoating composition B.
 25. A process for making an article having coatedand cured thereon a thermosetting powder coating composition A asdefined in claim 6, comprising the steps of: a. applying thethermosetting powder coating composition A to an article; b. heatingand/or radiating the thermosetting powder coating composition A forenough time and at a suitable temperature to cure said thermosettingpowder coating composition A to obtain the article having coated andcured thereon the thermosetting powder coating composition A.
 26. Aprocess for making an article having coated and cured thereon athermosetting powder coating composition B as defined in claim 9,comprising the steps of: a. applying the thermosetting powder coatingcomposition B, to an article; b. heating and/or radiating thethermosetting powder coating composition B for enough time and at asuitable temperature to cure said thermosetting powder coatingcomposition B to obtain the article having coated and cured thereon thethermosetting powder coating composition B.
 27. Use of: i) a branchedcarboxylic acid functional polyester resin P as defined in claim 1; orii) a thermosetting powder coating composition A; or iii) athermosetting powder coating composition B; or iv) a cured thermosettingpowder coating composition A; or v) a cured thermosetting powder coatingcomposition B; or vi) an article; in powder coatings, powder-in-mouldcoatings, 3D-printing, automotive applications, marine applications,aerospace applications, medical applications, defense applications,sports/recreational applications, architectural applications, bottlingapplications, household applications, machinery applications, canapplications, coil applications, energy applications, textileapplications and electrical applications.
 28. Use of a branchedcarboxylic acid functional polyester resin P as defined in claim 1 formatt powder coatings.
 29. Use of a thermosetting powder coatingcomposition A as defined in claim 6 in 2K thermosetting powder coatingcompositions.
 30. Use of a thermosetting powder coating composition B asdefined in claim 9 for matt powder coatings.